Microbiocidal quinoline (thio)carboxamide derivatives

ABSTRACT

Compounds of the formula (I) 
     
       
         
         
             
             
         
       
     
     wherein the subsitiuents are as defined in claim  1.    
     Furthermore, the present invention relates to agrochemical compositions which comprise compounds of formula (I), to preparation of these compositions, and to the use of the compounds or compositions in agriculture or horticulture for combating, preventing or controlling infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, in particular fungi.

The present invention relates to microbiocidal quinoline(thio)carboxamide derivatives, e.g. as active ingredients, which havemicrobiocidal activity, in particular fungicidal activity. The inventionalso relates to preparation of these quinoline (thio)carboxamidederivatives, to intermediates useful in the preparation of thesequinoline (thio)carboxamide derivatives, to the preparation of theseintermediates, to agrochemical compositions which comprise at least oneof the quinoline (thio)carboxamide derivatives, to preparation of thesecompositions and to the use of the quinoline (thio)carboxamidederivatives or compositions in agriculture or horticulture forcontrolling or preventing infestation of plants, harvested food crops,seeds or non-living materials by phytopathogenic microorganisms, inparticular fungi.

Certain fungicidal quinoline (thio)carboxamide compounds are describedin WO04039783.

It has now surprisingly been found that certain novel quinoline(thio)carboxamide derivatives have favourable fungicidal properties.

The present invention therefore provides compounds of formula (I)

wherein

X is O or S;

R₁ is hydrogen, halogen, methyl, methoxy or cyano;

R₂ and R₃ are each independently hydrogen, halogen or methyl;

R₄ is hydrogen, cyano, C₁-C₄ alkyl, or C₃-C₄ cycloalkyl, wherein thealkyl and cycloalkyl, may be optionally substituted with 1 to 3substituents independently selected from halogen, cyano, C₁-C₃ alkyl,C₁-C₃ alkoxy and C₁-C₃ alkylthio;

R₅ and R₆ are each independently selected from hydrogen, halogen, C₁-C₄alkyl, C₁-C₄ alkoxy and C₁-C₄ alkylthio; or

R₅ and R₆ together with the carbon atom to which they are attachedrepresent C═O, C═NOR_(c), C₃-C₅ cycloalkyl or C₂-C₅alkenyl, wherein thecycloalkyl and alkenyl may be optionally substituted with 1 to 3substituents independently selected from halogen, cyano, C₁-C₃ alkyl,C₁-C₃ alkoxy and C₁-C₃ alkylthio;

R₇ is hydrogen, C₁-C₅ alkyl, C₃-C₅ cycloalkyl, C₂-C₅ alkenyl, C₃-C₅cycloalkenyl, or C₂-C₅ alkynyl, wherein the alkyl, cycloalkyl, alkenyl,alkynyl, cycloalkenyl may be optionally substituted with 1 to 4substituents independently selected from halogen, cyano, C₁-C₃ alkyl,C₁-C₃ alkoxy, hydroxyl and C₁-C₃ alkylthio;

R₅ and R₉ are each independently selected from hydrogen, halogen, C₁-C₄alkyl and C₁-C₄ alkoxy; or

R₅ and R₉ together with the carbon atom to which they are attachedrepresent C₃-C₅ cycloalkyl, wherein the cycloalkyl may be optionallysubstituted with 1 to 3 substituents independently selected fromhalogen, cyano, C₁-C₃ alkyl, C₁-C₃ alkoxy and C₁-C₃ alkylthio;

each R₁₀ independently represents halogen, nitro, cyano, formyl, C₁-C₅alkyl, C₂-C₅ alkenyl, C₂-C₅ alkynyl, C₃-C₆ cycloalkyl, C₁-C₅ alkoxy,C₃-C₅ alkenyloxy, C₃-C₅ alkynyloxy, C₁-C₅ alkylthio, —C(═NOROC₁-C₅alkyl,or C₁-C₅ alkylcarbonyl, wherein the alkyl, cycloalkyl, alkenyl, alkynyl,alkoxy, alkenyloxy, alkynyloxy and alkylthio may be optionallysubstituted with 1 to 5 substituents independently selected fromhalogen, C₁-C₃ alkyl, C₁-C₃ alkoxy, cyano and C₁-C₃ alkylthio; n is 0,1, 2, 3, 4 or 5;

each R_(c) is independently selected from hydrogen, C₁-C₄ alkyl, C₂-C₄alkenyl, C₃-C₄ alkynyl, C₃-C₄cycloalkyl(C₁-C₂)alkyl and C₃-C₄cycloalkyl, wherein the alkyl, cycloalkyl, alkenyl and alkynyl groupsmay be optionally substituted with 1 to 3 substituents independentlyselected from halogen and cyano;

R₁₁ is hydrogen, halogen, methyl, methoxy or cyano;

R₁₂ and R₁₃ are each independently selected from hydrogen, halogen,methyl, methoxy or hydroxyl;

and salts and/or N-oxides thereof;

provided that the compound is not one of the following compounds:

In a second aspect the present invention provides an agrochemicalcomposition comprising a compound of formula (I).

Compounds of formula (I) may be used to control phytopathogenicmicroorganisms. Thus, in order to control a phytopathogen a compound offormula (I), or a composition comprising a compound of formula (I),according to the invention may be applied directly to the phytopathogen,or to the locus of a phytopathogen, in particular to a plant susceptibleto attack by phytopathogens.

Thus, in a third aspect the present invention provides the use of acompound of formula (I), or a composition comprising a compound offormula (I), as described herein to control a phytopathogen.

In a further aspect the present invention provides a method ofcontrolling phytopathogens, comprising applying a compound of formula(I), or a composition comprising a compound of formula (I), as describedherein to said phytopathogen, or to the locus of said phytopathogen, inparticular to a plant susceptible to attack by a phytopathogen.

Compounds of formula (I) are particularly effective in the control ofphytopathogenic fungi.

Thus, in a yet further aspect the present invention provides the use ofa compound of formula (I), or a composition comprising a compound offormula (I), as described herein to control phytopathogenic fungi.

In a further aspect the present invention provides a method ofcontrolling phytopathogenic fungi, comprising applying a compound offormula (I), or a composition comprising a compound of formula (I), asdescribed herein to said phytopathogenic fungi, or to the locus of saidphytopathogenic fungi, in particular to a plant susceptible to attack byphytopathogenic fungi.

Where substituents are indicated as being optionally substituted, thismeans that they may or may not carry one or more identical or differentsubstituents, e.g. one to three substituents. Normally not more thanthree such optional substituents are present at the same time. Where agroup is indicated as being substituted, e.g. alkyl, this includes thosegroups that are part of other groups, e.g. the alkyl in alkylthio.

The term “halogen” refers to fluorine, chlorine, bromine or iodine,preferably fluorine, chlorine or bromine.

Alkyl substituents (either alone or as part of a larger group, such asalkoxy-, alkylthio-) may be straight-chained or branched. Alkyl on itsown or as part of another substituent is, depending upon the number ofcarbon atoms mentioned, for example, methyl, ethyl, n-propyl, n-butyl,n-pentyl, n-hexyl and the isomers thereof, for example, iso-propyl,iso-butyl, sec-butyl, tert-butyl or iso-amyl.

Alkenyl substituents (either alone or as part of a larger group, eg.alkenyloxy) can be in the form of straight or branched chains, and thealkenyl moieties, where appropriate, can be of either the (E)- or(Z)-configuration. Examples are vinyl and allyl. The alkenyl groups arepreferably C₂-C₆, more preferably C₂-C₄ and most preferably C₂-C₃alkenyl groups.

Alkynyl substituents (either alone or as part of a larger group, eg.alkynyloxy) can be in the form of straight or branched chains. Examplesare ethynyl and propargyl. The alkynyl groups are preferably C₂-C₆, morepreferably C₂-C₄ and most preferably C₂-C₃ alkynyl groups.

Cycloalkyl substituents may be saturated or partially unsaturated,preferably fully saturated, and are, for example, cyclopropyl,cyclobutyl, cyclopentyl or cyclohexyl.

Haloalkyl groups (either alone or as part of a larger group, eg.haloalkyloxy) may contain one or more identical or different halogenatoms and, for example, may stand for CH₂Cl, CHCl₂, CCl₃, CH₂F, CHF₂,CF₃, CF₃CH₂, CH₃CF₂, CF₃CF₂ or CCl₃CCl₂.

Haloalkenyl groups (either alone or as part of a larger group, eg.haloalkenyloxy) are alkenyl groups, respectively, which are substitutedwith one or more of the same or different halogen atoms and are, forexample, 2,2-difluorovinyl or 1,2-dichloro-2-fluoro-vinyl.

Haloalkynyl groups (either alone or as part of a larger group, eg.haloalkynyloxy) are alkynyl groups, respectively, which are substitutedwith one or more of the same or different halogen atoms and are, forexample, 1-chloro-prop-2-ynyl.

Alkoxy means a radical —OR, where R is alkyl, e.g. as defined above.Alkoxy groups include, but are not limited to, methoxy, ethoxy,1-methylethoxy, propoxy, butoxy, 1-methylpropoxy and 2-methylpropoxy.

Cyano means a —CN group.

Amino means an —NH₂ group.

Hydroxyl or hydroxy stands for a —OH group.

Aryl groups (either alone or as part of a larger group, such as e.g.aryloxy, aryl-alkyl) are aromatic ring systems which can be in mono-,bi- or tricyclic form. Examples of such rings include phenyl, naphthyl,anthracenyl, indenyl or phenanthrenyl. Preferred aryl groups are phenyland naphthyl, phenyl being most preferred. Where an aryl moiety is saidto be substituted, the aryl moiety is preferably substituted by one tofour substituents, most preferably by one to three substituents.

Heteroaryl groups (either alone or as part of a larger group, such ase.g. heteroaryloxy, heteroaryl-alkyl) are aromatic ring systemscontaining at least one heteroatom and consisting either of a singlering or of two or more fused rings. Preferably, single rings willcontain up to three heteroatoms and bicyclic systems up to fourheteroatoms which will preferably be chosen from nitrogen, oxygen andsulfur. Examples of monocyclic groups include pyridyl, pyridazinyl,pyrimidinyl, pyrazinyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl (e.g.[1,2,4] triazolyl), furanyl, thiophenyl, oxazolyl, isoxazolyl,oxadiazolyl, thiazolyl, isothiazolyl and thiadiazolyl. Examples ofbicyclic groups include purinyl, quinolinyl, cinnolinyl, quinoxalinyl,indolyl, indazolyl, benzimidazolyl, benzothiophenyl and benzothiazolyl.Monocyclic heteroaryl groups are preferred, pyridyl being mostpreferred. Where a heteroaryl moiety is said to be substituted, theheteroaryl moiety is preferably substituted by one to four substituents,most preferably by one to three substituents.

Heterocyclyl groups or heterocyclic rings (either alone or as part of alarger group, such as heterocyclyl-alkyl) are non-aromatic ringstructures containing up to 10 atoms including one or more (preferablyone, two or three) heteroatoms selected from O, S and N. Examples ofmonocyclic groups include, oxetanyl, 4,5-dihydro-isoxazolyl, thietanyl,pyrrolidinyl, tetrahydrofuranyl, [1,3]dioxolanyl, piperidinyl,piperazinyl, [1,4]dioxanyl, imidazolidinyl, [1,3,5]oxadiazinanyl,hexahydro-pyrimidinyl, [1,3,5]triazinanyl and morpholinyl or theiroxidised versions such as 1-oxo-thietanyl and 1,1-dioxo-thietanyl.Examples of bicyclic groups include 2,3-dihydro-benzofuranyl,benzo[1,4]dioxolanyl, benzo[1,3]dioxolanyl, chromenyl, and2,3-dihydro-benzo[1,4]dioxinyl. Where a heterocyclyl moiety is said tobe substituted, the heterocyclyl moiety is preferably substituted by oneto four substituents, most preferably by one to three substituents.

The presence of one or more possible asymmetric carbon atoms in acompound of formula (I) means that the compounds may occur in opticallyisomeric forms, i.e. enantiomeric or diastereomeric forms. Alsoatropisomers may occur as a result of restricted rotation about a singlebond. Formula (I) is intended to include all those possible isomericforms and mixtures thereof. The present invention includes all thosepossible isomeric forms and mixtures thereof for a compound of formula(I). Likewise, formula (I) is intended to include all possibletautomers. The present invention includes all possible tautomeric formsfor a compound of formula (I).

In each case, the compounds of formula (I) according to the inventionare in free form, in oxidized form as a N-oxide or in salt form, e.g. anagronomically usable salt form.

N-oxides are oxidized forms of tertiary amines or oxidized forms ofnitrogen containing heteroaromatic compounds. They are described forinstance in the book “Heterocyclic N-oxides” by A. Albini and S. Pietra,CRC Press, Boca Raton 1991.

Preferred values of X, R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁,R₁₂, R₁₃, n and R_(c) are, in any combination thereof, as set out below:

Preferably X is O.

Preferably R₁ is hydrogen, fluoro, chloro, methyl, or cyano.

More preferably R₁ is hydrogen, fluoro, methyl, or cyano.

Most preferably R₁ is hydrogen or fluoro.

Preferably R₂ and R₃ are each independently hydrogen or methyl.

More preferably R₂ is hydrogen and R₃ is hydrogen or methyl; or R₂ ishydrogen or methyl and R₃ is hydrogen.

Most preferably R₂ and R₃ are both hydrogen.

Preferably R₄ is hydrogen, cyano, C₁-C₃ alkyl, or cyclopropyl, whereinthe alkyl and cycloalkyl, may be optionally substituted with 1 to 3substituents independently selected from fluoro, chloro, cyano, methyl,methoxy and methylthio.

More preferably R₄ is hydrogen, cyano, methyl or ethyl, wherein themethyl and ethyl may be optionally substituted with 1 to 3 substituentsindependently selected from fluoro and methoxy.

Most preferably R₄ is methyl or ethyl (wherein the methyl and ethyl maybe optionally substituted with 1 to 3 fluoro substituents or methoxy).

Preferably R₅ and R₆ are each independently selected from hydrogen,fluoro, C₁-C₂ alkyl, C₁-C₂ alkoxy and C₁-C₂ alkylthio; or R₅ and R₆together with the carbon atom to which they are attached represent C═Oor cyclopropyl, wherein the cyclopropyl may be optionally substitutedwith 1 to 2 substituents independently selected from fluoro, methyl andcyano.

More preferably R₅ and R₆ are each independently selected from hydrogen,fluoro, methyl, methoxy and methylthio; or R₅ and R₆ together with thecarbon atom to which they are attached represent cyclopropyl.

Most preferably R₅ and R₆ are each independently selected from hydrogenand fluoro.

Preferably R₇ is C₁-C₄ alkyl, C₃-C₄ cycloalkyl, C₂-C₄ alkenyl, or C₂-C₃alkynyl, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, may beoptionally substituted with 1 to 3 substituents independently selectedfrom fluoro, chloro, cyano, methyl, hydroxyl and methylthio.

More preferably R₇ is C₁-C₄ alkyl, C₃-C₄ cycloalkyl, or C₂-C₄ alkenyl,wherein the alkyl, cycloalkyl and alkenyl may be optionally substitutedwith 1 to 3 substituents independently selected from fluoro, chloro,hydroxyl, cyano and methyl.

Most preferably R₇ is methyl, ethyl, n-propyl, iso-propyl, sec-butyl,tert-butyl, C₃-C₄ cycloalkyl, or C₂-C₄ alkenyl, wherein the methyl,ethyl, n-propyl, iso-propyl, sec-butyl, tert-butyl, cycloalkyl andalkenyl may be optionally substituted with 1 to 3 substituentsindependently selected from fluoro, chloro and methyl.

Preferably R₅ and R₉ are each independently selected from hydrogen,fluoro, C₁-C₂ alkyl and C₁-C₂ alkoxy; or R₅ and R₉ together with thecarbon atom to which they are attached represent cyclopropyl, whereinthe cyclopropyl may be optionally substituted with 1 to 2 substituentsindependently selected from fluoro, cyano, and methyl.

More preferably R₅ and R₉ are each independently selected from hydrogen,fluoro and methyl; or R₅ and R₉ together with the carbon atom to whichthey are attached represent cyclopropyl.

Most preferably R₅ and R₉ are each independently selected from hydrogenor fluoro.

Preferably each R₁₀ independently represents halogen, cyano, C₁-C₃alkyl, C₂-C₃ alkenyl, C₂-C₃ alkynyl, cyclopropyl, methoxy, allyloxy,propargyloxy, or C₁-C₂ alkylthio, wherein the alkyl, cyclopropyl,alkenyl, alkynyl, methoxy, allyloxy, propargyloxy and alkylthio may beoptionally substituted with 1 to 3 substituents independently selectedfrom fluoro, chloro, methyl, and cyano; n is 0, 1, 2 or 3.

More preferably each R₁₀ independently represents fluoro, chloro, cyano,methyl, cyclopropyl, methoxy or methylthio, wherein the methyl,cyclopropyl, methoxy and methylthio may be optionally substituted with 1to 3 substituents independently selected from fluoro and chloro; n is 0,1 or 2.

Most preferably each R₁₀ independently represents fluoro, chloro, cyanoor methyl, wherein the methyl, cyclopropyl, methoxy and methylthio maybe optionally substituted with 1 to 3 fluoro substituents; n is 0, 1 or2.

Preferably each R_(c) is independently selected from hydrogen, methyl,ethyl, allyl, propargyl, and cyclopropylmethyl, wherein the methyl,ethyl, allyl, propargyl, and cyclopropylmethyl groups may be optionallysubstituted with 1 to 3 substituents independently selected from fluoroand chloro.

Most preferably each R_(c) is independently selected from methyl, ethyl,allyl, propargyl, and cyclopropylmethyl, wherein the methyl, ethyl,allyl, propargyl, and cyclopropylmethyl groups may be optionallysubstituted with 1 to 3 substituents independently selected from fluoroand chloro.

Preferably R₁₁ is hydrogen, fluoro, chloro, methyl or cyano.

More preferably R₁₁ is hydrogen, fluoro, methyl or chloro.

Most preferably R₁₁ is hydrogen or fluoro.

Preferably R₁₂ and R₁₃ are each independently selected from hydrogen,fluoro, methyl and hydroxyl.

More preferably R₁₂ and R₁₃ are each independently selected fromhydrogen, fluoro and methyl.

Most preferably R₁₂ and R₁₃ are both hydrogen.

Embodiments according to the invention are provided as set out below.

Embodiment 1 provides compounds of formula (I), or a salt or N-oxidethereof, as defined above.

Embodiment 2 provides compounds according to embodiment 1, or a salt orN-oxide thereof, wherein R₁ is hydrogen, fluoro, chloro, methyl, orcyano.

Embodiment 3 provides compounds according to embodiment 1 or 2, or asalt or N-oxide thereof, wherein R₂ and R₃ are each independentlyhydrogen or methyl.

Embodiment 4 provides compounds according to any one of embodiments 1, 2or 3, or a salt or N-oxide thereof, wherein R₄ is hydrogen, cyano, C₁-C₃alkyl, or cyclopropyl, wherein the alkyl and cycloalkyl, may beoptionally substituted with 1 to 3 substituents independently selectedfrom fluoro, chloro, cyano, methyl, methoxy, and methylthio.

Embodiment 5 provides compounds according to any one of embodiments 1,2, 3 or 4, or a salt or N-oxide thereof, wherein R₅ and R₆ are eachindependently selected from hydrogen, fluoro, C₁-C₂ alkyl, C₁-C₂ alkoxyand C₁-C₂ alkylthio; or R₅ and R₆ together with the carbon atom to whichthey are attached represent C═O or cyclopropyl, wherein the cyclopropylmay be optionally substituted with 1 to 2 substituents independentlyselected from fluoro, methyl and cyano.

Embodiment 6 provides compounds according to any one of embodiments 1,2, 3, 4, or 5, or a salt or N-oxide thereof, wherein R₇ is C₁-C₄ alkyl,C₃-C₄ cycloalkyl, C₂-C₄ alkenyl, or C₂-C₃ alkynyl, wherein the alkyl,cycloalkyl, alkenyl, alkynyl, may be optionally substituted with 1 to 3substituents independently selected from fluoro, chloro, cyano, methyl,hydroxyl and methylthio.

Embodiment 7 provides compounds according to any one of embodiments 1,2, 3, 4, 5, or 6, or a salt or N-oxide thereof, wherein R₅ and R₉ areeach independently selected from hydrogen, fluoro, C₁-C₂ alkyl and C₁-C₂alkoxy; or R₅ and R₉ together with the carbon atom to which they areattached represent cyclopropyl, wherein the cyclopropyl may beoptionally substituted with 1 to 2 substituents independently selectedfrom fluoro, cyano, and methyl.

Embodiment 8 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, or 7, or a salt or N-oxide thereof, wherein each R₁₀independently represents halogen, cyano, C₁-C₃ alkyl, C₂-C₃ alkenyl,C₂-C₃ alkynyl, cyclopropyl, methoxy, allyloxy, propargyloxy, or C₁-C₂alkylthio, wherein the alkyl, cyclopropyl, alkenyl, alkynyl, methoxy,allyloxy, propargyloxy and alkylthio may be optionally substituted with1 to 3 substituents independently selected from fluoro, chloro, methyl,and cyano; n is 0, 1, 2 or 3.

Embodiment 9 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, or 8, or a salt or N-oxide thereof, wherein each R, isindependently selected from hydrogen, methyl, ethyl, allyl, propargyl,and cyclopropylmethyl, wherein the methyl, ethyl, allyl, propargyl, andcyclopropylmethyl groups may be optionally substituted with 1 to 3substituents independently selected from fluoro and chloro.

Embodiment 10 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, or 9, or a salt or N-oxide thereof, wherein R₁ ishydrogen, fluoro, methyl, or cyano.

Embodiment 11 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9 or 10, or a salt or N-oxide thereof, wherein R₂is hydrogen and R₃ is hydrogen or methyl; or R₂ is hydrogen or methyland R₃ is hydrogen.

Embodiment 12 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, or a salt or N-oxide thereof, whereinR₄ is hydrogen, cyano, methyl or ethyl, wherein the methyl and ethyl maybe optionally substituted with 1 to 3 substituents independentlyselected from fluoro and methoxy.

Embodiment 13 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, or a salt or N-oxide thereof,wherein R₅ and R₆ are each independently selected from hydrogen, fluoro,methyl, methoxy and methylthio; or R₅ and R₆ together with the carbonatom to which they are attached represent cyclopropyl.

Embodiment 14 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13, or a salt or N-oxide thereof,wherein R₇ is C₁-C₄ alkyl, C₃-C₄ cycloalkyl, or C₂-C₄ alkenyl, whereinthe alkyl, cycloalkyl and alkenyl may be optionally substituted with 1to 3 substituents independently selected from fluoro, chloro, hydroxyl,cyano and methyl.

Embodiment 15 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14, or a salt or N-oxidethereof, wherein R₅ and R₉ are each independently selected fromhydrogen, fluoro and methyl; or R₅ and R₉ together with the carbon atomto which they are attached represent cyclopropyl.

Embodiment 16 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15, or a salt or N-oxidethereof, wherein each R₁₀ independently represents fluoro, chloro,cyano, methyl, cyclopropyl, methoxy or methylthio, wherein the methyl,cyclopropyl, methoxy and methylthio may be optionally substituted with 1to 3 substituents independently selected from fluoro and chloro; n is 0,1 or 2.

Embodiment 17 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16, or a salt orN-oxide thereof, wherein each R_(c) is independently selected frommethyl, ethyl, allyl, propargyl, and cyclopropylmethyl, wherein themethyl, ethyl, allyl, propargyl, and cyclopropylmethyl groups may beoptionally substituted with 1 to 3 substituents independently selectedfrom fluoro and chloro.

Embodiment 18 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 or 17, or a salt orN-oxide thereof, wherein R₁ is hydrogen or fluoro.

Embodiment 19 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18, or a saltor N-oxide thereof, wherein R₂ and R₃ are both hydrogen.

Embodiment 20 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 or 19, or asalt or N-oxide thereof, wherein R₄ is methyl or ethyl (wherein themethyl and ethyl may be optionally substituted with 1 to 3 fluorosubstituents).

Embodiment 21 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20,ora salt or N-oxide thereof, wherein R₅ and R₆ are each independentlyselected from hydrogen and fluoro.

Embodiment 22 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 or21, or a salt or N-oxide thereof, wherein R₇ is methyl, ethyl, n-propyl,iso-propyl, sec-butyl, tert-butyl, C₃-C₄ cycloalkyl, or C₂-C₄ alkenyl,wherein the methyl, ethyl, n-propyl, iso-propyl, sec-butyl, tert-butyl,cycloalkyl and alkenyl may be optionally substituted with 1 to 3substituents independently selected from fluoro, chloro and methyl.

Embodiment 23 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21or 22, or a salt or N-oxide thereof, wherein R₅ and R₉ are eachindependently selected from hydrogen or fluoro.

Embodiment 24 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22 or 23, or a salt or N-oxide thereof, wherein each R₁₀ independentlyrepresents fluoro, chloro, cyano or methyl, wherein the methyl,cyclopropyl, methoxy and methylthio may be optionally substituted with 1to 3 fluoro substituents; n is 0, 1 or 2.

Embodiment 25 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23 or 24, or a salt or N-oxide thereof, wherein R₁₁ is hydrogen,fluoro, chloro, methyl or cyano. Embodiment 26 provides compoundsaccording to any one of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11,12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25, or a salt orN-oxide thereof, wherein R₁₂ and R₁₃ are each independently selectedfrom hydrogen, fluoro, methyl and hydroxyl.

Embodiment 27 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25 or 26, or a salt or N-oxide thereof, wherein R₁₁ ishydrogen, fluoro, methyl or chloro.

Embodiment 28 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26 or 27, or a salt or N-oxide thereof, wherein R₁₂ andR₁₃ are each independently selected from hydrogen, fluoro and methyl.

Embodiment 29 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26, 27 or 28, or a salt or N-oxide thereof, wherein R₁₁is hydrogen or fluoro.

Embodiment 30 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26, 27, 28 or 29, or a salt or N-oxide thereof, whereinR₁₂ and R₁₃ are both hydrogen.

One group of compounds according to the invention are those of formula(I′):

wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, n andR_(c) are as defined for compounds of formula (I), or a salt or N-oxidethereof. Preferred definitions of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉,R₁₀, R₁₁, R₁₂, R₁₃, n and R_(c) are as defined for compounds of formula(I).

One group of compounds according to the invention are those of formula(I″):

wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, n andR_(c) are as defined for compounds of formula (I), or a salt or N-oxidethereof. Preferred definitions of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉,R₁₀, R₁₁, R₁₂, R₁₃, n and R_(c) are as defined for compounds of formula(I).

A preferred group of compounds according to the invention are those offormula (I-1) which are compounds of formula (I) wherein X is O or S; R₁is hydrogen, fluoro, chloro, methyl, or cyano; R₂ and R₃ are eachindependently hydrogen or methyl; R₄ is hydrogen, cyano, C₁-C₃ alkyl, orcyclopropyl, wherein the alkyl and cycloalkyl, may be optionallysubstituted with 1 to 3 substituents independently selected from fluoro,chloro, cyano, methyl, methoxy, and methylthio; R₅ and R₆ are eachindependently selected from hydrogen, fluoro, C₁-C₂ alkyl, C₁-C₂ alkoxyand C₁-C₂ alkylthio; or R₅ and R₆ together with the carbon atom to whichthey are attached represent C═O or cyclopropyl, wherein the cyclopropylmay be optionally substituted with 1 to 2 substituents independentlyselected from fluoro, methyl and cyano; R₇ is C₁-C₄ alkyl, C₃-C₄cycloalkyl, C₂-C₄ alkenyl, or C₂-C₃ alkynyl, wherein the alkyl,cycloalkyl, alkenyl, alkynyl, may be optionally substituted with 1 to 3substituents independently selected from fluoro, chloro, cyano, methyl,hydroxyl and methylthio; R₈ and R₉ are each independently selected fromhydrogen, fluoro, C₁-C₂ alkyl and C₁-C₂ alkoxy; or R₈ and R₉ togetherwith the carbon atom to which they are attached represent cyclopropyl,wherein the cyclopropyl may be optionally substituted with 1 to 2substituents independently selected from fluoro, cyano, and methyl; eachR₁₀ independently represents halogen, cyano, C₁-C₃ alkyl, C₂-C₃ alkenyl,C₂-C₃ alkynyl, cyclopropyl, methoxy, allyloxy, propargyloxy, or C₁-C₂alkylthio, wherein the alkyl, cyclopropyl, alkenyl, alkynyl, methoxy,allyloxy, propargyloxy and alkylthio may be optionally substituted with1 to 3 substituents independently selected from fluoro, chloro, methyl,and cyano; n is 0, 1, 2 or 3; R₁₁ is hydrogen, fluoro, chloro, methyl orcyano; and R₁₂ and R₁₃ are each independently selected from hydrogen,fluoro, methyl and hydroxyl; or a salt or N-oxide thereof.

One group of compounds according to this embodiment are compounds offormula (1-1a) which are compounds of formula (I-1) wherein X is O.

Another group of compounds according to this embodiment are compounds offormula (I-1b) which are compounds of formula (I-1) wherein X is S.

A further preferred group of compounds according to the invention arethose of formula (I-2) which are compounds of formula (I) wherein X is Oor S; R₁ is hydrogen, fluoro, methyl, or cyano; R₂ is hydrogen and R₃ ishydrogen or methyl; or R₂ is hydrogen or methyl and R₃ is hydrogen; R₄is hydrogen, cyano, methyl or ethyl, wherein the methyl and ethyl may beoptionally substituted with 1 to 3 substituents independently selectedfrom fluoro and methoxy; R₅ and R₆ are each independently selected fromhydrogen, fluoro, methyl, methoxy and methylthio; or R₅ and R₆ togetherwith the carbon atom to which they are attached represent cyclopropyl;R₇ is C₁-C₄ alkyl, C₃-C₄ cycloalkyl, or C₂-C₄ alkenyl, wherein thealkyl, cycloalkyl and alkenyl may be optionally substituted with 1 to 3substituents independently selected from fluoro, chloro, hydroxyl, cyanoand methyl; R₈ and R₉ are each independently selected from hydrogen,fluoro and methyl; or R₈ and R₉ together with the carbon atom to whichthey are attached represent cyclopropyl; each R₁₀ independentlyrepresents fluoro, chloro, cyano, methyl, cyclopropyl, methoxy ormethylthio, wherein the methyl, cyclopropyl, methoxy and methylthio maybe optionally substituted with 1 to 3 substituents independentlyselected from fluoro and chloro; n is 0, 1 or 2; R₁₁ is hydrogen,fluoro, methyl or chloro; and R₁₂ and R₁₃ are each independentlyselected from hydrogen, fluoro and methyl; or a salt or N-oxide thereof.

One group of compounds according to this embodiment are compounds offormula (I-2a) which are compounds of formula (I-2) wherein X is O.

Another group of compounds according to this embodiment are compounds offormula (I-2b) which are compounds of formula (I-2) wherein X is S.

A further preferred group of compounds according to the invention arethose of formula (I-3) which are compounds of formula (I) wherein X is Oor S; R₁ is hydrogen or fluoro; R₂ and R₃ are both hydrogen; R₄ ismethyl or ethyl (wherein the methyl and ethyl may be optionallysubstituted with 1 to 3 fluoro substituents); R₅ and R₆ are eachindependently selected from hydrogen and fluoro; R₇ is methyl, ethyl,n-propyl, iso-propyl, sec-butyl, tert-butyl, C₃-C₄ cycloalkyl, or C₂-C₄alkenyl, wherein the methyl, ethyl, n-propyl, iso-propyl, sec-butyl,tert-butyl, cycloalkyl and alkenyl may be optionally substituted with 1to 3 substituents independently selected from fluoro, chloro and methyl;R₅ and R₉ are each independently selected from hydrogen or fluoro; eachR₁₀ independently represents fluoro, chloro, cyano or methyl, whereinthe methyl, cyclopropyl, methoxy and methylthio may be optionallysubstituted with 1 to 3 fluoro substituents; n is 0, 1 or 2; and R₁₁ ishydrogen or fluoro; R₁₂ and R₁₃ are both hydrogen; or a salt or N-oxidethereof.

One group of compounds according to this embodiment are compounds offormula (I-3a) which are compounds of formula (I-3) wherein X is O.

Another group of compounds according to this embodiment are compounds offormula (I-3b) which are compounds of formula (I-3) wherein X is S.

Compounds according to the invention may possess any number of benefitsincluding, inter alia, advantageous levels of biological activity forprotecting plants against diseases that are caused by fungi or superiorproperties for use as agrochemical active ingredients (for example,greater biological activity, an advantageous spectrum of activity, anincreased safety profile, improved physico-chemical properties, orincreased biodegradability).

Specific examples of compounds of formula (I) are illustrated in theTables A1 to A13 below:

Table A1 provides 248 compounds of formula (I-a)

wherein R₁, R₂ and R₃ are all H and R₁₁, R₁₂, R₁₃ are all H

and wherein the values of R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ and n (if R₁₀and n are present) are as defined in Table Z below:

TABLE Z Entry R₄ R₅ R₆ R₇ R₈ R₉ R₁₀ 1 H H H CH₃ H H — 2 H H H CH₂CH₃ H H— 3 H H H CH₂CH₂CH₃ H H — 4 H H H CH₂CH₂CF₃ H H — 5 H H H CH(CH₃)₂ H H —6 H H H CH═CH₂ H H — 7 H H H C(CH₃)═CH₂ H H — 8 H H H C(Cl)═CH₂ H H — 9H H H C(CH₃)═CF₂ H H — 10 H H H C(F)═CH₂ H H — 11 H H H C(CH₃)₃ H H — 12H H H CF(CH₃)₂ H H — 13 H H H C(OH)(CH₃)₂ H H — 14 H H H C(CN)(CH₃)₂ H H— 15 H H H C(SCH₃)(CH₃)₂ H H — 16 H H H CF₃ H H — 17 H H H CHF₂ H H — 18H H H CF₂CH₃ H H — 19 H H H CF₂Cl H H — 20 H H H CH═CF₂ H H — 21 H H HCH═C(CH₃)H H H — 22 H H H CH═C(CH₃)₂ H H — 23 H H H cyclopropyl H H — 24H H H 1-methylcyclopropyl H H — 25 H H H 1-fluorocyclopropyl H H — 26 HH H 1-cyanocyclopropyl H H — 27 H H H 1-Methylthiocyclopropyl H H — 28 HH H cyclobutyl H H — 29 H H H 1-fluorocyclobutyl H H — 30 H H H3,3-difluorocyclobutyl H H — 31 CH₃ H H CH₃ H H — 32 CH₃ H H CH₂CH₃ H H— 33 CH₃ H H CH₂CH₂CH₃ H H — 34 CH₃ H H CH₂CH₂CF₃ H H — 35 CH₃ H HCH(CH₃)₂ H H — 36 CH₃ H H CH═CH₂ H H — 37 CH₃ H H C(CH₃)═CH₂ H H — 38CH₃ H H C(Cl)═CH₂ H H — 39 CH₃ H H C(CH₃)═CF₂ H H — 40 CH₃ H H C(F)═CH₂H H — 41 CH₃ H H C(CH₃)₃ H H — 42 CH₃ H H CF(CH₃)₂ H H — 43 CH₃ H HC(OH)(CH₃)₂ H H — 44 CH₃ H H C(CN)(CH₃)₂ H H — 45 CH₃ H H C(SCH₃)(CH₃)₂H H — 46 CH₃ H H CF₃ H H — 47 CH₃ H H CHF₂ H H — 48 CH₃ H H CF₂CH₃ H H —49 CH₃ H H CF₂Cl H H — 50 CH₃ H H CH═CF₂ H H — 51 CH₃ H H CH═C(CH₃)H H H— 52 CH₃ H H CH═C(CH₃)₂ H H — 53 CH₃ H H cyclopropyl H H — 54 CH₃ H H1-methylcyclopropyl H H — 55 CH₃ H H 1-fluorocyclopropyl H H — 56 CH₃ HH 1-cyanocyclopropyl H H — 57 CH₃ H H 1-Methylthiocyclopropyl H H — 58CH₃ H H cyclobutyl H H — 59 CH₃ H H 1-fluorocyclobutyl H H — 60 CH₃ H H3,3-difluorocyclobutyl H H — 61 H CH₃ H CH₃ H H — 62 H CH₃ CH₃ CH₃ H H —63 H cyclopropyl CH₃ H H — 64 H CH₃ CH₃ CH₂CH₃ H H — 65 H cyclopropylCH₂CH₃ H H — 66 CH₃ H H H H H — 67 CH₃ H H F H H — 68 CH₃ H H Cl H H —69 CH₂CH₃ H H H H H — 70 CH₂CH₃ H H F H H — 71 CH₂CH₃ H H Cl H H — 72CH₂CH₃ H H CH₃ H H — 73 CH₂CH₃ H H CH₂CH₃ H H — 74 CH₂CH₃ H H CH₂CH₂CH₃H H — 75 CH₂CH₃ H H CH(CH₃)₂ H H — 76 CH₂CH₃ H H CH═CH₂ H H — 77 CH₂CH₃H H C(CH₃)═CH₂ H H — 78 CH₂CH₃ H H C(CH₃)₃ H H — 79 CH₂CH₃ H H CF(CH₃)₂H H — 80 CH₂CH₃ H H C(CN)(CH₃)₂ H H — 81 CH₂CH₃ H H C(SCH₃)(CH₃)₂ H H —82 CH₂CH₃ H H CF₃ H H — 83 CH₂CH₃ H H CHF₂ H H — 84 CH₂CH₃ H H CF₂CH₃ HH — 85 CH₂CH₃ H H cyclopropyl H H — 86 CH₂CH₃ H H 1-methylcyclopropyl HH — 87 CH₂CH₃ H H 1-fluorocyclopropyl H H — 88 CH₂CH₃ H H1-cyanocyclopropyl H H — 89 CH₂CH₃ H H 1-Methylthiocyclopropyl H H — 90CH₂CH₃ H H cyclobutyl H H — 91 CH₂CH₃ H H 1-fluorocyclobutyl H H — 92CH₂CH₃ H H 3,3-difluorocyclobutyl H H — 93 CN H H CH₃ H H — 94 CN H HCH₂CH₃ H H — 95 CN H H CH₂CH₂CH₃ H H — 96 CN H H CH(CH₃)₂ H H — 97 CN HH C(CH₃)₃ H H — 98 CN H H CF(CH₃)₂ H H — 99 CN H H CF₃ H H — 100 CH₂OCH₃H H CH₃ H H — 101 CH₂OCH₃ H H CH₂CH₂CF₃ H H — 102 CH₂OCH₃ H H CH(CH₃)₂ HH — 103 CH₂OCH₃ H H CH═CH₂ H H — 104 CH₂OCH₃ H H C(CH₃)═CH₂ H H — 105CH₂OCH₃ H H C(CH₃)₃ H H — 106 CH₂OCH₃ H H CF(CH₃)₂ H H — 107 CH₂OCH₃ H HCF₃ H H — 108 CH₂OCH₃ H H CHF₂ H H — 109 CH₂OCH₃ H H CF₂CH₃ H H — 110CH₂OCH₃ H H CF₂Cl H H — 111 CH₂OCH₃ H H CH═CF₂ H H — 112 CH₂OCH₃ H Hcyclopropyl H H — 113 CH₂OCH₃ H H 1-methylcyclopropyl H H — 114 CH₂OCH₃H H 1-fluorocyclopropyl H H — 115 CH₂OCH₃ H H 1-cyanocyclopropyl H H —116 CH₃ F F H H H — 117 CH₃ F F F H H — 118 CH₃ F F CH₃ H H — 119 CH₃ FF CH₂CH₃ H H — 120 CH₃ F F CH₂CH₂CH₃ H H — 121 CH₃ F F CH(CH₃)₂ H H —122 CH₃ F F C(CH₃)₃ H H — 123 CH₃ F F cyclopropyl H H — 124 CH₃ F F1-methylcyclopropyl H H — 125 CH₃ F F cyclobutyl H H — 126 CH₃ CH₃ CH₃ HH H — 127 CH₃ CH₃ CH₃ F H H — 128 CH₃ CH₃ CH₃ CH₃ H H — 129 CH₃ CH₃ CH₃CH₂CH₃ H H — 130 CH₃ CH₃ CH₃ CH(CH₃)₂ H H — 131 CH₃ CH₃ CH₃ CH═CH₂ H H —132 CH₃ CH₃ CH₃ C(CH₃)═CH₂ H H — 133 CH₃ CH₃ CH₃ cyclopropyl H H — 134CH₃ cyclopropyl H H H — 135 CH₃ cyclopropyl F H H — 136 CH₃ cyclopropylCl H H — 137 CH₃ cyclopropyl CH₃ H H — 138 CH₃ cyclopropyl CH₂CH₃ H H —139 CH₃ cyclopropyl CH(CH₃)₂ H H — 140 CH₃ cyclopropyl CH═CH₂ H H — 141CH₃ cyclopropyl C(CH₃)═CH₂ H H — 142 CH₃ cyclopropyl cyclopropyl H H —143 CH₂CH₃ F F H H H — 144 CH₂CH₃ F F F H H — 145 CH₂CH₃ F F CH₃ H H —146 CH₂CH₃ F F CH₂CH₃ H H — 147 CH₂CH₃ F F CH₂CH₂CH₃ H H — 148 CH₂CH₃ FF CH(CH₃)₂ H H — 149 CH₂CH₃ F F C(CH₃)₃ H H — 150 CH₂CH₃ F F cyclopropylH H — 151 CH₂CH₃ F F 1-methylcyclopropyl H H — 152 CH₂CH₃ F F cyclobutylH H — 153 CH₂CH₃ CH₃ CH₃ H H H — 154 CH₂CH₃ CH₃ CH₃ F H H — 155 CH₂CH₃CH₃ CH₃ Cl H H — 156 CH₂CH₃ CH₃ CH₃ CH₃ H H — 157 CH₂CH₃ CH₃ CH₃ CH₂CH₃H H — 158 CH₂CH₃ CH₃ CH₃ CH(CH₃)₂ H H — 159 CH₂CH₃ CH₃ CH₃ CH═CH₂ H H —160 CH₂CH₃ CH₃ CH₃ C(CH₃)═CH₂ H H — 161 CH₂CH₃ CH₃ CH₃ cyclopropyl H H —162 CH₂CH₃ cyclopropyl H H H — 163 CH₂CH₃ cyclopropyl F H H — 164 CH₂CH₃cyclopropyl Cl H H — 165 CH₂CH₃ cyclopropyl CH₃ H H — 166 CH₂CH₃cyclopropyl CH₂CH₃ H H — 167 CH₂CH₃ cyclopropyl CH(CH₃)₂ H H — 168CH₂CH₃ cyclopropyl CH═CH₂ H H — 169 CH₂CH₃ cyclopropyl C(CH₃)═CH₂ H H —170 CH₂CH₃ cyclopropyl cyclopropyl H H — 171 CH₃ H H CH(CH₃)₂ H H 2-F172 CH₃ H H CH(CH₃)₂ H H 3-F 173 CH₃ H H CH(CH₃)₂ H H 4-F 174 CH₃ H HCH(CH₃)₂ H H 2-Cl 175 CH₃ H H CH(CH₃)₂ H H 3-Cl 176 CH₃ H H CH(CH₃)₂ H H4-Cl 177 CH₃ H H CH(CH₃)₂ H H 2-CH₃ 178 CH₃ H H CH(CH₃)₂ H H 3-CH₃ 179CH₃ H H CH(CH₃)₂ H H 4-CH₃ 180 CH₃ H H CH(CH₃)₂ H H 2-CN 181 CH₃ H HCH(CH₃)₂ H H 3-CN 182 CH₃ H H CH(CH₃)₂ H H 4-CN 183 CH₃ H H CH(CH₃)₂ H H2-SCH₃ 184 CH₃ H H CH(CH₃)₂ H H 3-SCH₃ 185 CH₃ H H CH(CH₃)₂ H H 4-SCH₃186 CH₃ H H CH(CH₃)₂ F F — 187 CH₃ H H CH(CH₃)₂ CH₃ CH₃ — 188 CH₃ H HCH(CH₃)₂ cyclopropyl — 189 CH₃ H H CF₃ H H 2-F 190 CH₃ H H CF₃ H H 3-F191 CH₃ H H CF₃ H H 4-F 192 CH₃ H H CF₃ H H 2-Cl 193 CH₃ H H CF₃ H H3-Cl 194 CH₃ H H CF₃ H H 4-Cl 195 CH₃ H H CF₃ H H 2-CH₃ 196 CH₃ H H CF₃H H 3-CH₃ 197 CH₃ H H CF₃ H H 4-CH₃ 198 CH₃ H H CF₃ H H 2-CN 199 CH₃ H HCF₃ H H 3-CN 200 CH₃ H H CF₃ H H 4-CN 201 CH₃ H H CF₃ H H 2-SCH₃ 202 CH₃H H CF₃ H H 3-SCH₃ 203 CH₃ H H CF₃ H H 4-SCH₃ 204 CH₃ H H C(CH₃)═CH₂ H H2-F 205 CH₃ H H C(CH₃)═CH₂ H H 3-F 206 CH₃ H H C(CH₃)═CH₂ H H 4-F 207CH₃ H H C(CH₃)═CH₂ H H 2-Cl 208 CH₃ H H C(CH₃)═CH₂ H H 3-Cl 209 CH₃ H HC(CH₃)═CH₂ H H 4-Cl 210 CH₃ H H C(CH₃)═CH₂ H H 2-CH₃ 211 CH₃ H HC(CH₃)═CH₂ H H 3-CH₃ 212 CH₃ H H C(CH₃)═CH₂ H H 4-CH₃ 213 CH₃ H HC(CH₃)═CH₂ H H 2-CN 214 CH₃ H H C(CH₃)═CH₂ H H 3-CN 215 CH₃ H HC(CH₃)═CH₂ H H 4-CN 216 CH₃ H H C(CH₃)═CH₂ H H 2-SCH₃ 217 CH₃ H HC(CH₃)═CH₂ H H 3-SCH₃ 218 CH₃ H H C(CH₃)═CH₂ H H 4-SCH₃ 219 CH₃ H HCF(CH₃)₂ H H 2-F 220 CH₃ H H CF(CH₃)₂ H H 3-F 221 CH₃ H H CF(CH₃)₂ H H4-F 222 CH₃ H H CF(CH₃)₂ H H 2-Cl 223 CH₃ H H CF(CH₃)₂ H H 3-Cl 224 CH₃H H CF(CH₃)₂ H H 4-Cl 225 CH₃ H H CF(CH₃)₂ H H 2-CH₃ 226 CH₃ H HCF(CH₃)₂ H H 3-CH₃ 227 CH₃ H H CF(CH₃)₂ H H 4-CH₃ 228 CH₃ H H CF(CH₃)₂ HH 2-CN 229 CH₃ H H CF(CH₃)₂ H H 3-CN 230 CH₃ H H CF(CH₃)₂ H H 4-CN 231CH₃ H H CF(CH₃)₂ H H 2-SCH₃ 232 CH₃ H H CF(CH₃)₂ H H 3-SCH₃ 233 CH₃ H HCF(CH₃)₂ H H 4-SCH₃ 234 CH₃ H H CF₂CH₃ H H 2-F 235 CH₃ H H CF₂CH₃ H H3-F 236 CH₃ H H CF₂CH₃ H H 4-F 237 CH₃ H H CF₂CH₃ H H 2-Cl 238 CH₃ H HCF₂CH₃ H H 3-Cl 239 CH₃ H H CF₂CH₃ H H 4-Cl 240 CH₃ H H CF₂CH₃ H H 2-CH₃241 CH₃ H H CF₂CH₃ H H 3-CH₃ 242 CH₃ H H CF₂CH₃ H H 4-CH₃ 243 CH₃ H HCF₂CH₃ H H 2-CN 244 CH₃ H H CF₂CH₃ H H 3-CN 245 CH₃ H H CF₂CH₃ H H 4-CN246 CH₃ H H CF₂CH₃ H H 2-SCH₃ 247 CH₃ H H CF₂CH₃ H H 3-SCH₃ 248 CH₃ H HCF₂CH₃ H H 4-SCH₃

Table A2 provides 248 compounds of formula (I-a) wherein R₁₁, R₁₂, R₁₃are all H, R₁ is fluoro, R₂ and R₃ are H and wherein the values of R₄,R₅, R₆, R₇, R₅, R₈ and R₁₀ are as defined in Table Z above.

Table A3 provides 248 compounds of formula (I-a) wherein R₁₁, R₁₂, R₁₃are all H, R₁ is chloro, R₂ and R₃ are H and wherein the values of R₄,R₅, R₆, R₇, R₈, R₉ and R₁₀ are as defined in Table Z above.

Table A4 provides 248 compounds of formula (I-a) wherein R₁₁, R₁₂, R₁₃are all H, R₁ is bromo, R₂ and R₃ are H and wherein the values of R₄,R₅, R₆, R₇, R₈, R₉ and R₁₀ are as defined in Table Z above.

Table A5 provides 248 compounds of formula (I-a) wherein R₁₁, R₁₂, R₁₃are all H, R₁ is methyl, R₂ and R₃ are H and wherein the values of R₄,R₅, R₆, R₇, R₈, R₉ and R₁₀ are as defined in Table Z above.

Table A6 provides 248 compounds of formula (I-a) wherein R₁₁, R₁₂, R₁₃are all H, R₁ is cyano, R₂ and R₃ are H and wherein the values of R₄,R₅, R₆, R₇, R₈, R₉ and R₁₀ are as defined in Table Z above.

Table A7 provides 248 compounds of formula (I-a) wherein R₁₁ is fluoro,R₁ is H, R₂ and R₃ are H and wherein the values of R₄, R₅, R₆, R₇, R₈,R₉ and R₁₀ are as defined in Table Z above.

Table A8 provides 248 compounds of formula (I-a) wherein R₁₁, R₁₂, R₁₃are all H, R₂ is methyl, R₁ and R₃ are H and wherein the values of R₄,R₅, R₆, R₇, R₈, R₉ and R₁₀ are as defined in Table Z above.

Table A9 provides 248 compounds of formula (I-a) wherein R₁₁, R₁₂, R₁₃are all H, R₃ is methyl, R₁ and R₂ are H and wherein the values of R₄,R₅, R₆, R₇, R₈, R₉ and R₁₀ are as defined in Table Z above.

Table A10 provides 248 compounds of formula (I-a) wherein R₁₁, R₁₂, R₁₃are all H, R₂ is methyl, R₁ is fluoro and R₃ is H and wherein the valuesof R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ are as defined in Table Z above.

Table A11 provides 248 compounds of formula (I-a) wherein R₁₁, R₁₂, R₁₃are all H, R₃ is methyl, R₁ is fluoro and R₂ is H and wherein the valuesof R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ are as defined in Table Z above.

Table A12 provides 248 compounds of formula (I-a) wherein R₁₂, R₁₃ areH, R₂ and R₃ are H, R₁ and R₁₁ are fluoro, and wherein the values of R₄,R₅, R₆, R₇, R₈, R₉ and R₁₀ are as defined in Table Z above.

Table A13 provides 248 compounds of formula (I-b)

wherein R₁₁, R₁₂, R₁₃, R₁, R₂ and R₃ are all H

and wherein the values of R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ are as definedin Table Z above.

Table A14 provides 248 compounds of formula (I-b) wherein R₁ is fluoro,R₁₁, R₁₂, R₁₃, R₂ and R₃ are H and wherein the values of R₄, R₅, R₆, R₇,R₈, R₉ and R₁₀ are as defined in Table Z above.

Compounds of the present invention can be made as shown in the followingschemes, in which, unless otherwise stated, the definition of eachvariable is as defined above for a compound of formula (I).

A shown in scheme 1, compounds of general formula (I-a) wherein R₁, R₂,R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃ and n are as defined forcompounds of formula (I) and X is O can be prepared by the reaction ofcompounds of formula (II) wherein R₁, R₂, R₃, R₁₁, R₁₂ and R₁₃ are asdefined for compounds of formula (I) with amines of formula (III)wherein R₄, R₅, R₆, R₇, R₈, R₉, R₁₀ and n are as defined for compoundsof formula (I).

Among the various reported methods for this transformation, the mostwidely applied involve treatment of carboxylic acid (II) with anactivating agent like thionyl chloride or an amide coupling reagent likedicyclohexylcarbodiimide in an inert organic solvent liketetrahydrofuran (THF) or dimethylformamide (DMF) and reaction with amine(III) in the presence of a catalyst like dimethylaminopyridine asdescribed in Chem. Soc. Rev., 2009, 606-631 or Tetrahedron 2005,10827-10852.

As shown in scheme 2, compounds of general formula (I-a) wherein X is Ocan also be prepared by the reaction of compounds of formula (IV) and(V) in the presence of a Brönsted acid like sulphuric acid ortrifluoromethane sulfonic acid, in a solvent like dichloromethane oracetic acid at temperatures between −20° C. and +50° C. as described inEur. J. Org. Chem. 2015, 2727-2732 and Synthesis 2000, 1709-1712.

Alternatively, compounds of general formula (I-a) wherein X is O canalso be prepared by the reaction of compounds of formula (VI) withamines of formula (III), carbon monoxide, a base like triethylamine orpotassium carbonate and a suitably supported transitional metal catalystlike palladium in an inert organic solvent like 1,4-dioxane at atemperature between 20° C. and 110° C. as described in Org. Lett., 2014,4296-4299 (and references therein) and shown in scheme 3.

Alternatively, compounds of general formula (1-a) wherein X is O canalso be prepared by the reaction of organometallic compounds of formula(Via) with isocyanates of formula (IIIa) in an inert organic solventlike diethyl ether or THF at temperatures between −78° C. and +40° C. asdescribed in Angew. Chem. Int. Ed. 2012, 9173-9175 and shown in scheme4.

The preparation of organometallic compounds of formula (VIa) fromcompounds of formula (VI) by lithium-halogen exchange with an alkyllithium reagent like s-butyl lithium or magnesium-halogen exchange withtri n-butyl magnesate in an ethereal solvent like THF at temperaturesbetween −90° C. and +20° C. is generally known to a person skilled inthe art, and is described in synthetic chemistry texts such as March'sAdvanced Organic Chemistry.

As shown in scheme 5, carboxylic acids of formula (II) can be preparedby various methods and many are commercially available. Among the manyreported methods for their preparation, the following have been widelyapplied:

1) Transformation of anilines of formula (VII) to quinolones of formula(VIIb) by reaction with a malonate derivative of formula (VIIa) in aninert solvent like diphenyl ether at temperatures between 100° C. and260° C. as described in US 20070015758, followed by well-knownfunctional group interconversion which is generally known to a personskilled in the art and also described in WO 2007133637.

2) Transformation of compounds of formula (VI) to organometallicintermediates of formula (VIa) by lithium-halogen exchange with an alkyllithium reagent like s-butyl lithium or magnesium-halogen exchange withtri n-butyl magnesate in an ethereal solvent like THF at temperaturesbetween −90° C. and +20° C. and subsequent reaction with CO₂.

3) Transformation of compounds of formula (VI) in the presence of acarbon monoxide source, a base like triethylamine, water or anequivalent thereof and a suitably ligated transition metal catalystcontaining for example palladium as described in J. Am. Chem. Soc. 2013,2891-2894 (and references therein) or Tetrahedron 2003, 8629-8640.

As shown in scheme 6, compounds of formula (IV) can be prepared fromcompounds of formula (VI) by treatment with a cyanide source like zinccyanide in the presence of a palladium, nickel or copper catalyst in aninert solvent like DMF at temperatures between 20° C. and 150° C. asdescribed in J. Org. Chem. 2011, 665-668 or Bull. Chem. Soc. Jpn. 1993,2776-8.

As shown in scheme 7, compounds of formula (VI) can be prepared bytreatment of compounds of formula (VIa) with a halogenating agent likeN-iodosuccinimide, bromine or chlorine in an inert solvent as describedin WO 2005113539 or JP 2001322979. Alternatively, compounds of formula(VI) can be prepared by treatment of propargylated anilines of formula(VIb) with a halogenating agent like iodine in an inert solvent likeacetonitrile and a base like sodium hydrogen carbonate at temperaturesbetween 0° C. and 80° C. as described in Org. Lett. 2005, 763-766.

The preparation of propargylated anilines of formula (VIb) from thecorresponding commercially available anilines is trivial to a personskilled in the art and described in March's Advanced Organic Chemistry,Smith and March, 6^(th) edition, Wiley, 2007.

The synthesis of compounds of formula (Via) is generally known to aperson skilled in the art and a large selection of compounds iscommercially available.

As shown in scheme 8, compounds of formula (V) can be prepared fromcarbonyl compounds of formula (Va) or (Vc) by treatment with anorganometallic species of formula (Vb) or (Vd) respectively where X islithium, an aluminum- or a magnesium-salt, in an inert solvent likediethyl ether at temperatures between −90° C. and 60° C.

The general preparation, handling and reactivity of reagents withformula (Vb) and (Vd) is described in March's Advanced OrganicChemistry, Smith and March, 6^(th) edition, Wiley, 2007 and is generallyknown to a person skilled in the art. A large selection of compounds offormula (Va) and (Vc), where R₄,R₅,R₆,R₇,R₈,R₉ and R₁₀ as defined in theabove, are also commercially available and their syntheses are welldescribed in the scientific literature and synthetic chemistry text(such as March's Advanced Organic Chemistry) and, further, are generallyknown to a person skilled in the art.

As shown in scheme 9, amines of formula (III) can be prepared fromcompounds of formula (Vc) by condensation with tertbutyl sulfinamide inthe presence of a dehydrating agent like Ti(OEt)4 to form sulfimines offormula (Ve) which can then be treated with an organometallic reagent offormula (Vd), where X is lithium, an aluminum- or a magnesium-salt, inan inert solvent like THF at temperatures between −78° C. and +70° C.,followed by an acidic hydrolysis of the sulfonamide; a sequencegenerally known to a person skilled in the art and also described inChem. Rev. 2010, 3600-3740.

Alternatively, amines of formula (III) can be prepared from compounds offormula (Vcc) by condensation with tertbutyl sulfinamide in the presenceof a dehydrating agent like Ti(OEt)4 to form sulfimines of formula (Vee)which can then be treated with an organometallic reagent of formula(Vdd), where X is lithium, an aluminum- or a magnesium-salt, in an inertsolvent like THF at temperatures between −78° C. and +70° C., followedby an acidic hydrolysis of the sulfonamide.

Alternatively, amines of formula (III) can be also prepared fromalcohols of formula (V) by treatment with a strong acid like sulfuricacid in the presence of chloroacetonitrile in an organic solvent likeacetic acid at temperatures between −10° C. and 50° C. to give amides offormula (IIIb) which can be deprotected with thiourea in an organicsolvent like ethanol or acetic acid at temperatures between 20° C. and100° C. as described in Synthesis 2000, 1709-1712 and shown in scheme10.

Alternatively, amines of formula (III) can be also prepared fromcarboxylic acids of formula (IX) through an intermediary isocyanate offormula (IIIa) or a carbamate of formula (IIIc), where R₁₄ is C₁-C₄alkyl, is which can be hydrolyzed with aqueous acid or base attemperatures between 0° C. and 100° C. as shown in scheme 11.

Among the various protocols reported for the transformation of acid (IX)to isocyanate (IIIa), the following have found wide spread application:

1) Treatment of acid (IX) with diphenylphosphoryl azide and an aminebase like tributylamine in an inert organic solvent like toluene attemperatures between 50° C. and 120° C. to give isocyanate (IIIa) asdescribed in Aust. J. Chem., 1973, 1591-3.

2) Treatment of acid (IX) with an activating agent like thionyl chlorideor propylphosphonic anhydride in the presence of an azide source likesodium azide and an amine base like triethyl amine in an inert solventlike THF at temperatures between 20° C. and 100° C. as described inSynthesis 2011, 1477-1483.

3) Conversion of acid (IX) to the corresponding hydroxamic acids whichcan then be treated with a dehydrating agent like para-toluenesulfonylchloride and a base like triethylamine in an inert organic solvent liketoluene at temperatures between 20° C. and 120° C.

4) Conversion of acid (IX) to the corresponding primary carboxamidewhich can then be treated with an oxidizing agent such asdiacetoxyiodobenzene and an acid such as trifluoroacetic acid orpara-toluenesulfonic acid in a solvent like acetonitrile at temperaturesbetween 0° C. and 100° C. as described in J. Org. Chem. 1984, 4212-4216.

5) Conversion of acid (IX) to the corresponding primary carboxamidewhich can then be treated with an oxidizing agent such as bromine and abase such as sodium hydroxide in a solvent like water or methanol attemperatures between 0° C. and 100° C.

A person skilled in the art will appreciate that carboxylic acids offormula (IX) can be prepared from the corresponding esters. Similarly aperson skilled in the art will appreciate that the alpha position ofthese esters can be functionalized by deprotonation with a strong baselike lithium diisopropylamine in an inert solvent like THF attemperatures between −78° C. and 20° C. followed by reaction with anelectrophilic reagent like an alkyl iodide as described in March'sAdvanced Organic Chemistry, Smith and March, 6^(th) edition, Wiley,2007. This reaction can be repeated to prepare acids of formula (IX)from commercially available esters.

Alternatively, amines of formula (III) can be also prepared by reductionof nitro compounds of formula (Xa) with a reducing agent like iron in anorganic solvent like acetic acid at temperatures between 20° C. and 120°C. as shown in scheme 12. Nitro compounds of formula (Xa) in turn can beprepared from simpler nitro compounds of formula (X) by treatment with abenzyl bromide and a base like sodium tert-butoxide in the presence of acopper catalyst in an inert solvent like hexanes at temperatures between20° C. and 100° C. as described in J. Am. Chem. Soc. 2012, 9942-9945.

The synthesis of compounds of formula (X) is generally known to a personskilled in the art and a large selection is commercially available.

Alternatively, amines of formula (III) can be also prepared by treatmentof compounds of formula (V) with trimethylsilyl azide and a lewis acidcatalyst like B(C₆F₆)₃ in an inert solvent like toluene at temperaturesbetween 0° C. and 100° C. as described in J. Am. Chem. Soc. 2015,9555-9558, followed by reduction of the intermediary azides of formula(XI) with a reducing agent like hydrogen/palladium in an organic solventlike methanol at temperatures between 0° C. and 80° C. as shown as shownin scheme 13.

As shown in scheme 14, compounds of general formula (I-b) wherein X is Scan be prepared from compounds of general formula (I-a) wherein X is Oby treatment with a deoxothionating agent like P₄S₁₀ or Lawesson reagentin an inert organic solvent like toluene at temperatures between 20° C.and 150° C.

Alternatively, the compounds of formula (I-a), wherein wherein R₁, R₂,R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃ and n are as defined forcompounds of formula (I) and X is O, can be obtained by transformationof a compound of formula I-i, wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈,R₉, R₁₁, R₁₂, R₁₃ and n are as defined for formula (I) and X is O and Zrepresents chlorine, bromine or iodine in a solvent, in the presence ofor absence of a base, and in the presence of a coupling reagent and ametal catalyst. There are no particular limitations on the couplingagent, catalyst, solvent and bases, provided it is used in ordinarycoupling reactions, such as those described in “Cross-CouplingReactions: A Practical Guide (Topics in Current Chemistry)”, edited byNorio Miyaura and S. L. Buchwald (editions Springer), or“Metal-Catalyzed Cross-Coupling Reactions”, edited by Armin de Meijereand François Diederich (editions WILEY-VCH). This is shown in Scheme 15.

Alternatively, the compounds of formula (I-a) wherein R₁, R₂, R₃, R₄,R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃ and n are as defined forcompounds of formula (I) and X is O, can be obtained by transformationof another, closely related, compound of formula (I-a) using standardsynthesis techniques known to the person skilled in the art.Non-exhaustive examples include oxidation reactions, reductionreactions, hydrolysis reactions, coupling reactions, aromaticnucleophilic or electrophilic substitution reactions, nucleophilicsubstitution reactions, nucleophilic addition reactions, andhalogenation reactions.

Certain intermediates described in the above schemes are novel and assuch form a further aspect of the invention.

The compounds of formula (I) can be used in the agricultural sector andrelated fields of use e.g. as active ingredients for controlling plantpests or on non-living materials for control of spoilage microorganismsor organisms potentially harmful to man. The novel compounds aredistinguished by excellent activity at low rates of application, bybeing well tolerated by plants and by being environmentally safe. Theyhave very useful curative, preventive and systemic properties and may beused for protecting numerous cultivated plants. The compounds of formula(I) can be used to inhibit or destroy the pests that occur on plants orparts of plants (fruit, blossoms, leaves, stems, tubers, roots) ofdifferent crops of useful plants, while at the same time protecting alsothose parts of the plants that grow later e.g. from phytopathogenicmicroorganisms.

It is also possible to use compounds of formula (I) as fungicide. Theterm “fungicide” as used herein means a compound that controls,modifies, or prevents the growth of fungi. The term “fungicidallyeffective amount” means the quantity of such a compound or combinationof such compounds that is capable of producing an effect on the growthof fungi. Controlling or modifying effects include all deviation fromnatural development, such as killing, retardation and the like, andprevention includes barrier or other defensive formation in or on aplant to prevent fungal infection.

It is also possible to use compounds of formula (I) as dressing agentsfor the treatment of plant propagation material, e.g., seed, such asfruits, tubers or grains, or plant cuttings (for example rice), for theprotection against fungal infections as well as against phytopathogenicfungi occurring in the soil. The propagation material can be treatedwith a composition comprising a compound of formula (I) before planting:seed, for example, can be dressed before being sown. The compounds offormula (I) can also be applied to grains (coating), either byimpregnating the seeds in a liquid formulation or by coating them with asolid formulation. The composition can also be applied to the plantingsite when the propagation material is being planted, for example, to theseed furrow during sowing. The invention relates also to such methods oftreating plant propagation material and to the plant propagationmaterial so treated.

Furthermore the compounds according to present invention can be used forcontrolling fungi in related areas, for example in the protection oftechnical materials, including wood and wood related technical products,in food storage, in hygiene management.

In addition, the invention could be used to protect non-living materialsfrom fungal attack, e.g. lumber, wall boards and paint.

Compounds of formula (I) and fungicidal compositions containing them maybe used to control plant diseases caused by a broad spectrum of fungalplant pathogens. They are effective in controlling a broad spectrum ofplant diseases, such as foliar pathogens of ornamental, turf, vegetable,field, cereal, and fruit crops.

These fungi and fungal vectors of disease, as well as phytopathogenicbacteria and viruses, which may be controlled are for example:

Absidia corymbifera, Alternaria spp, Aphanomyces spp, Ascochyta spp,Aspergillus spp. including A. flavus, A. fumigatus, A. nidulans, A.niger, A. terrus, Aureobasidium spp. including A. pullulans, Blastomycesdermatitidis, Blumeria graminis, Bremia lactucae, Botryosphaeria spp.including B. dothidea, B. obtusa, Botrytis spp. inclusing B. cinerea,Candida spp. including C. albicans, C. glabrata, C. krusei, C.lusitaniae, C. parapsilosis, C. tropicalis, Cephaloascus fragrans,Ceratocystis spp, Cercospora spp. including C. arachidicola,Cercosporidium personatum, Cladosporium spp, Claviceps purpurea,

Coccidioides immitis, Cochliobolus spp, Colletotrichum spp. including C.musae,

Cryptococcus neoformans, Diaporthe spp, Didymella spp, Drechslera spp,Elsinoe spp,

Epidermophyton spp, Erwinia amylovora, Erysiphe spp. including E.cichoracearum,

Eutypa lata, Fusarium spp. including F. culmorum, F. graminearum, F.langsethiae, F. moniliforme, F. oxysporum, F. proliferatum, F.subglutinans, F. solani, Gaeumannomyces graminis, Gibberella fujikuroi,Gloeodes pomigena, Gloeosporium musarum, Glomerella cingulate,Guignardia bidwellii, Gymnosporangium juniperi-virginianae,Helminthosporium spp, Hemileia spp, Histoplasma spp. including H.capsulatum, Laetisaria fuciformis, Leptographium lindbergi, Leveillulataurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp,Monilinia spp, Mucor spp, Mycosphaerella spp. including M. graminicola,M. pomi, Oncobasidium theobromaeon, Ophiostoma piceae, Paracoccidioidesspp, Penicillium spp. including P. digitatum, P. italicum, Petriellidiumspp, Peronosclerospora spp. Including P. maydis, P. philippinensis andP. sorghi, Peronospora spp, Phaeosphaeria nodorum, Phakopsorapachyrhizi, Phellinus igniarus, Phialophora spp, Phoma spp, Phomopsisviticola, Phytophthora spp. including P. infestans, Plasmopara spp.including P. halstedii, P. viticola, Pleospora spp., Podosphaera spp.including P. leucotricha, Polymyxa graminis, Polymyxa betae,Pseudocercosporella herpotrichoides, Pseudomonas spp, Pseudoperonosporaspp. including P. cubensis, P. humuli, Pseudopeziza tracheiphila,Puccinia Spp. including P. hordei, P. recondita, P. striiformis, P.triticina, Pyrenopeziza spp, Pyrenophora spp, Pyricularia spp. includingP. oryzae, Pythium spp. including P. ultimum, Ramularia spp, Rhizoctoniaspp, Rhizomucor pusillus, Rhizopus arrhizus, Rhynchosporium spp,Scedosporium spp. including S. apiospermum and S. prolificans,Schizothyrium pomi,

Sclerotinia spp, Sclerotium spp, Septoria spp, including S. nodorum, S.tritici, Sphaerotheca macularis, Sphaerotheca fusca (Sphaerothecafuliginea), Sporothorix spp, Stagonospora nodorum, Stemphylium spp,Stereum hirsutum, Thanatephorus cucumeris, Thielaviopsis basicola,Tilletia spp, Trichoderma spp. including T. harzianum, T.pseudokoningii, T. viride,

Trichophyton spp, Typhula spp, Uncinula necator, Urocystis spp, Ustilagospp, Venturia spp. including V. inaequalis, Verticillium spp, andXanthomonas spp.

In particular, compounds of formula (I) and fungicidal compositionscontaining them may be used to control plant diseases caused by a broadspectrum of fungal plant pathogens in the Basidiomycete, Ascomycete,Oomycete and/or Deuteromycete, Blasocladiomycete, Chrytidiomycete,Glomeromycete and/or Mucoromycete classes.

These pathogens may include:

Oomycetes, including Phytophthora diseases such as those caused byPhytophthora capsici, Phytophthora infestans, Phytophthora sojae,Phytophthora fragariae, Phytophthora nicotianae, Phytophthora cinnamomi,Phytophthora citricola, Phytophthora citrophthora and Phytophthoraerythroseptica; Pythium diseases such as those caused by Pythiumaphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythiumirregulare and Pythium ultimum; diseases caused by Peronosporales suchas Peronospora destructor, Peronospora parasitica, Plasmopara viticola,Plasmopara halstedii, Pseudoperonospora cubensis, Albugo candida,Sclerophthora macrospora and Bremia lactucae; and others such asAphanomyces cochlioides, Labyrinthula zosterae, Peronosclerospora sorghiand Sclerospora graminicola.

Ascomycetes, including blotch, spot, blast or blight diseases and/orrots for example those caused by Pleosporales such as Stemphyliumsolani, Stagonospora tainanensis, Spilocaea oleaginea, Setosphaeriaturcica, Pyrenochaeta lycoperisici, Pleospora herbarum, Phomadestructiva, Phaeosphaeria herpotrichoides, Phaeocryptocus gaeumannii,Ophiosphaerella graminicola, Ophiobolus graminis, Leptosphaeriamaculans, Hendersonia creberrima, Helminthosporium triticirepentis,Setosphaeria turcica, Drechslera glycines, Didymella bryoniae,Cycloconium oleagineum, Corynespora cassiicola, Cochliobolus sativus,Bipolaris cactivora, Venturia inaequalis, Pyrenophora teres, Pyrenophoratritici-repentis, Alternaria alternata, Alternaria brassicicola,Alternaria solani and Alternaria tomatophila, Capnodiales such asSeptoria tritici, Septoria nodorum, Septoria glycines, Cercosporaarachidicola, Cercospora sojina, Cercospora zeae-maydis, Cercosporellacapsellae and Cercosporella herpotrichoides, Cladosporium carpophilum,Cladosporium effusum, Passalora fulva, Cladosporium oxysporum,Dothistroma septosporum, lsariopsis clavispora, Mycosphaerellafijiensis, Mycosphaerella graminicola, Mycovellosiella koepkeii,Phaeoisariopsis bataticola, Pseudocercospora vitis, Pseudocercosporellaherpotrichoides, Ramularia beticola, Ramularia collo-cygni,Magnaporthales such as Gaeumannomyces graminis, Magnaporthe grisea,Pyricularia oryzae, Diaporthales such as Anisogramma anomala,Apiognomonia errabunda, Cytospora platani, Diaporthe phaseolorum,Discula destructiva, Gnomonia fructicola, Greeneria uvicola, Melanconiumjuglandinum, Phomopsis viticola, Sirococcusclavigignenti-juglandacearum, Tubakia dryina, Dicarpella spp., Valsaceratosperma, and others such as Actinothyrium graminis, Ascochyta pisi,Aspergillus flavus, Aspergillus fumigatus, Aspergillus nidulans,Asperisporium caricae, Blumeriella jaapii, Candida spp., Capnodiumramosum, Cephaloascus spp., Cephalosporium gramineum, Ceratocystisparadoxa, Chaetomium spp., Hymenoscyphus pseudoalbidus, Coccidioidesspp., Cylindrosporium padi, aplocarpon malae, Drepanopeziza campestris,Elsinoe ampelina, Epicoccum nigrum, Epidermophyton spp., Eutypa lata,Geotrichum candidum, Gibellina cerealis, Gloeocercospora sorghi,Gloeodes pomigena, Gloeosporium perennans; Gloeotinia temulenta,Griphospaeria corticola, Kabatiella lini, Leptographium microsporum,Leptosphaerulinia crassiasca, Lophodermium seditiosum, Marssoninagraminicola, Microdochium nivale, Monilinia fructicola, Monographellaalbescens, Monosporascus cannonballus, Naemacyclus spp., Ophiostomanovo-ulmi, Paracoccidioides brasiliensis, Penicillium expansum,Pestalotia rhododendri, Petriellidium spp., Pezicula spp., Phialophoragregata, Phyllachora pomigena, Phymatotrichum omnivora, Physalosporaabdita, Plectosporium tabacinum, Polyscytalum pustulans, Pseudopezizamedicaginis, Pyrenopeziza brassicae, Ramulispora sorghi, Rhabdoclinepseudotsugae, Rhynchosporium secalis, Sacrocladium oryzae, Scedosporiumspp., Schizothyrium pomi, Sclerotinia sclerotiorum, Sclerotinia minor;Sclerotium spp., Typhula ishikariensis, Seimatosporium mariae,Lepteutypa cupressi, Septocyta ruborum, Sphaceloma perseae, Sporonemaphacidioides, Stigmina palmivora, Tapesia yallundae, Taphrina bullata,Thielviopsis basicola, Trichoseptoria fructigena, Zygophialajamaicensis; powdery mildew diseases for example those caused byErysiphales such as Blumeria graminis, Erysiphe polygoni, Uncinulanecator, Sphaerotheca fuligena, Podosphaera leucotricha, Podospaeramacularis Golovinomyces cichoracearum, LevelHula taurica, Microsphaeradiffusa, Oidiopsis gossypii, Phyllactinia guttata and Oidium arachidis;molds for example those caused by Botryosphaeriales such as Dothiorellaaromatica, Diplodia seriata, Guignardia bidwellii, Botrytis cinerea,Botryotinia allii, Botryotinia fabae, Fusicoccum amygdali, Lasiodiplodiatheobromae, Macrophoma theicola, Macrophomina phaseolina, Phyllostictacucurbitacearum; anthracnoses for example those caused by Glommerelalessuch as Colletotrichum gloeosporioides, Colletotrichum lagenarium,Colletotrichum gossypii, Glomerella cingulata, and Colletotrichumgraminicola; and wilts or blights for example those caused byHypocreales such as Acremonium strictum, Claviceps purpurea, Fusariumculmorum, Fusarium graminearum, Fusarium virguliforme, Fusariumoxysporum, Fusarium subglutinans, Fusarium oxysporum f.sp. cubense,Gerlachia nivale, Gibberella fujikuroi, Gibberella zeae, Gliocladiumspp., Myrothecium verrucaria, Nectria ramulariae, Trichoderma viride,Trichothecium roseum, and Verticillium theobromae.

Basidiomycetes, including smuts for example those caused byUstilaginales such as Ustilaginoidea virens, Ustilago nuda, Ustilagotritici, Ustilago zeae, rusts for example those caused by Puccinialessuch as Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporiumipomoeae, Hemileia vastatrix, Puccinia arachidis, Puccinia cacabata,Puccinia graminis, Puccinia recondita, Puccinia sorghi, Puccinia hordei,Puccinia striiformis f.sp. Hordei, Puccinia striiformis f.sp. Secalis,Pucciniastrum coryli, or Uredinales such as Cronartium ribicola,Gymnosporangium juniperi-viginianae, Melampsora medusae, Phakopsorapachyrhizi, Phragmidium mucronatum, Physopella ampelosidis, Tranzscheliadiscolor and Uromyces viciae-fabae; and other rots and diseases such asthose caused by Cryptococcus spp., Exobasidium vexans, Marasmiellusinoderma, Mycena spp., Sphacelotheca reiliana, Typhula ishikariensis,Urocystis agropyri, ltersonilia perplexans, Corticium invisum,Laetisaria fuciformis, Waitea circinata, Rhizoctonia solani,Thanetephorus cucurmeris, Entyloma dahliae, Entylomella microspora,Neovossia moliniae and Tilletia caries.

Blastocladiomycetes, such as Physoderma maydis.

Mucoromycetes, such as Choanephora cucurbitarum.; Mucor spp.; Rhizopusarrhizus,

As well as diseases caused by other species and genera closely relatedto those listed above.

In addition to their fungicidal activity, the compounds and compositionscomprising them may also have activity against bacteria such as Erwiniaamylovora, Erwinia caratovora, Xanthomonas campestris, Pseudomonassyringae, Strptomyces scabies and other related species as well ascertain protozoa.

Within the scope of present invention, target crops and/or useful plantsto be protected typically comprise perennial and annual crops, such asberry plants for example blackberries, blueberries, cranberries,raspberries and strawberries; cereals for example barley, maize (corn),millet, oats, rice, rye, sorghum triticale and wheat; fibre plants forexample cotton, flax, hemp, jute and sisal; field crops for examplesugar and fodder beet, coffee, hops, mustard, oilseed rape (canola),poppy, sugar cane, sunflower, tea and tobacco; fruit trees for exampleapple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pearand plum; grasses for example Bermuda grass, bluegrass, bentgrass,centipede grass, fescue, ryegrass, St. Augustine grass and Zoysia grass;herbs such as basil, borage, chives, coriander, lavender, lovage, mint,oregano, parsley, rosemary, sage and thyme; legumes for example beans,lentils, peas and soya beans; nuts for example almond, cashew, groundnut, hazelnut, peanut, pecan, pistachio and walnut; palms for exampleoil palm; ornamentals for example flowers, shrubs and trees; othertrees, for example cacao, coconut, olive and rubber; vegetables forexample asparagus, aubergine, broccoli, cabbage, carrot, cucumber,garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin,rhubarb, spinach and tomato; and vines for example grapes.

The useful plants and/or target crops in accordance with the inventioninclude conventional as well as genetically enhanced or engineeredvarieties such as, for example, insect resistant (e.g. Bt. and VIPvarieties) as well as disease resistant, herbicide tolerant (e.g.glyphosate- and glufosinate-resistant maize varieties commerciallyavailable under the trade names RoundupReady® and LibertyLinke) andnematode tolerant varieties. By way of example, suitable geneticallyenhanced or engineered crop varieties include the Stoneville 5599BRcotton and Stoneville 4892BR cotton varieties.

The term “useful plants” and/or “target crops” is to be understood asincluding also useful plants that have been rendered tolerant toherbicides like bromoxynil or classes of herbicides (such as, forexample, HPPD inhibitors, ALS inhibitors, for example primisulfuron,prosulfuron and trifloxysulfuron, EPSPS(5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS(glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase)inhibitors) as a result of conventional methods of breeding or geneticengineering. An example of a crop that has been rendered tolerant toimidazolinones, e.g. imazamox, by conventional methods of breeding(mutagenesis) is Clearfield® summer rape (Canola). Examples of cropsthat have been rendered tolerant to herbicides or classes of herbicidesby genetic engineering methods include glyphosate- andglufosinate-resistant maize varieties commercially available under thetrade names RoundupReady®, Herculex I® and LibertyLink®.

The term “useful plants” and/or “target crops” is to be understood asincluding those which naturally are or have been rendered resistant toharmful insects. This includes plants transformed by the use ofrecombinant DNA techniques, for example, to be capable of synthesisingone or more selectively acting toxins, such as are known, for example,from toxin-producing bacteria. Examples of toxins which can be expressedinclude δ-endotoxins, vegetative insecticidal proteins (Vip),insecticidal proteins of bacteria colonising nematodes, and toxinsproduced by scorpions, arachnids, wasps and fungi. An example of a cropthat has been modified to express the Bacillus thuringiensis toxin isthe Bt maize KnockOut® (Syngenta Seeds). An example of a crop comprisingmore than one gene that codes for insecticidal resistance and thusexpresses more than one toxin is VipCot® (Syngenta Seeds). Crops or seedmaterial thereof can also be resistant to multiple types of pests(so-called stacked transgenic events when created by geneticmodification). For example, a plant can have the ability to express aninsecticidal protein while at the same time being herbicide tolerant,for example Herculex I® (Dow AgroSciences, Pioneer Hi-BredInternational). The term “useful plants” and/or “target crops” is to beunderstood as including also useful plants which have been sotransformed by the use of recombinant DNA techniques that they arecapable of synthesising antipathogenic substances having a selectiveaction, such as, for example, the so-called “pathogenesis-relatedproteins” (PRPs, see e.g. EP-A-0 392 225). Examples of suchantipathogenic substances and transgenic plants capable of synthesisingsuch antipathogenic substances are known, for example, from EP-A-0 392225, WO 95/33818, and EP-A-0 353 191. The methods of producing suchtransgenic plants are generally known to the person skilled in the artand are described, for example, in the publications mentioned above.

Toxins that can be expressed by transgenic plants include, for example,insecticidal proteins from Bacillus cereus or Bacillus popilliae; orinsecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins,e.g. Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, orvegetative insecticidal proteins (Vip), e.g. Vip1, Vip2, Vip3 or Vip3A;or insecticidal proteins of bacteria colonising nematodes, for examplePhotorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens,Xenorhabdus nematophilus; toxins produced by animals, such as scorpiontoxins, arachnid toxins, wasp toxins and other insect-specificneurotoxins; toxins produced by fungi, such as Streptomycetes toxins,plant lectins, such as pea lectins, barley lectins or snowdrop lectins;agglutinins; proteinase inhibitors, such as trypsin inhibitors, serineprotease inhibitors, patatin, cystatin, papain inhibitors;ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin,luffin, saporin or bryodin; steroid metabolism enzymes, such as3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase,cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ionchannel blockers, such as blockers of sodium or calcium channels,juvenile hormone esterase, diuretic hormone receptors, stilbenesynthase, bibenzyl synthase, chitinases and glucanases.

Further, in the context of the present invention there are to beunderstood by δ-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2,Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins(Vip), for example Vip1, Vip2, Vip3 or Vip3A, expressly also hybridtoxins, truncated toxins and modified toxins. Hybrid toxins are producedrecombinantly by a new combination of different domains of thoseproteins (see, for example, WO 02/15701). Truncated toxins, for examplea truncated Cry1Ab, are known. In the case of modified toxins, one ormore amino acids of the naturally occurring toxin are replaced. In suchamino acid replacements, preferably non-naturally present proteaserecognition sequences are inserted into the toxin, such as, for example,in the case of Cry3A055, a cathepsin-G-recognition sequence is insertedinto a Cry3A toxin (see WO03/018810).

More examples of such toxins or transgenic plants capable ofsynthesising such toxins are disclosed, for example, in EP-A-0 374 753,WO93/07278, WO95/34656, EP-A-0 427 529, EP-A-451 878 and WO03/052073.

The processes for the preparation of such transgenic plants aregenerally known to the person skilled in the art and are described, forexample, in the publications mentioned above. Cryl-type deoxyribonucleicacids and their preparation are known, for example, from WO 95/34656,EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxin contained in the transgenic plants imparts to the plantstolerance to harmful insects. Such insects can occur in any taxonomicgroup of insects, but are especially commonly found in the beetles(Coleoptera), two-winged insects (Diptera) and butterflies(Lepidoptera).

Transgenic plants containing one or more genes that code for aninsecticidal resistance and express one or more toxins are known andsome of them are commercially available. Examples of such plants are:YieldGard® (maize variety that expresses a Cry1Ab toxin); YieldGardRootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGardPlus® (maize variety that expresses a Cry1Ab and a Cry3Bb1 toxin);Starlink® (maize variety that expresses a Cry9C toxin); Herculex I®(maize variety that expresses a Cry1Fa2 toxin and the enzymephosphinothricine N-acetyltransferase (PAT) to achieve tolerance to theherbicide glufosinate ammonium); NuCOTN 336® (cotton variety thatexpresses a Cry1Ac toxin); Bollgard I® (cotton variety that expresses aCry1Ac toxin); Bollgard Il® (cotton variety that expresses a Cry1Ac anda Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and aCry1Ab toxin); NewLeaf® (potato variety that expresses a Cry3A toxin);NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait),Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®.

Further examples of such transgenic crops are:

1. Bt11 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a truncated Cry1Ab toxin. Bt11 maize alsotransgenically expresses the enzyme PAT to achieve tolerance to theherbicide glufosinate ammonium.

2. Bt176 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a Cry1Ab toxin. Bt176 maize also transgenicallyexpresses the enzyme PAT to achieve tolerance to the herbicideglufosinate ammonium.

3. MIR604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. 15 Sauveur, France, registration number C/FR/96/05/10. Maize whichhas been rendered insect-resistant by transgenic expression of amodified Cry3A toxin. This toxin is Cry3A055 modified by insertion of acathepsin-G-protease recognition sequence. The preparation of suchtransgenic maize plants is described in WO 03/018810.

4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863expresses a Cry3Bb1 toxin and has resistance to certain Coleopterainsects.

5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/ES/96/02.

6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, registration number C/NL/00/10. Geneticallymodified maize for the expression of the protein Cryl F for achievingresistance to certain Lepidoptera insects and of the PAT protein forachieving tolerance to the herbicide glufosinate ammonium.

7. NK603×MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue deTervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03.Consists of conventionally bred hybrid maize varieties by crossing thegenetically modified varieties NK603 and MON 810. NK603×MON 810 Maizetransgenically expresses the protein CP4 EPSPS, obtained fromAgrobacterium sp. strain CP4, which imparts tolerance to the herbicideRoundup® (contains glyphosate), and also a Cry1Ab toxin obtained fromBacillus thuringiensis subsp. kurstaki which brings about tolerance tocertain Lepidoptera, include the European corn borer.

The term “locus” as used herein means fields in or on which plants aregrowing, or where seeds of cultivated plants are sown, or where seedwill be placed into the soil. It includes soil, seeds, and seedlings, aswell as established vegetation.

The term “plants” refers to all physical parts of a plant, includingseeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, andfruits.

The term “plant propagation material” is understood to denote generativeparts of the plant, such as seeds, which can be used for themultiplication of the latter, and vegetative material, such as cuttingsor tubers, for example potatoes. There may be mentioned for exampleseeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes andparts of plants. Germinated plants and young plants which are to betransplanted after germination or after emergence from the soil, mayalso be mentioned. These young plants may be protected beforetransplantation by a total or partial treatment by immersion. Preferably“plant propagation material” is understood to denote seeds.

Pesticidal agents referred to herein using their common name are known,for example, from “The Pesticide Manual”, 15th Ed., British CropProtection Council 2009.

The compounds of formula (I) may be used in unmodified form or,preferably, together with the adjuvants conventionally employed in theart of formulation. To this end they may be conveniently formulated inknown manner to emulsifiable concentrates, coatable pastes, directlysprayable or dilutable solutions or suspensions, dilute emulsions,wettable powders, soluble powders, dusts, granulates, and alsoencapsulations e.g. in polymeric substances. As with the type of thecompositions, the methods of application, such as spraying, atomising,dusting, scattering, coating or pouring, are chosen in accordance withthe intended objectives and the prevailing circumstances. Thecompositions may also contain further adjuvants such as stabilizers,antifoams, viscosity regulators, binders or tackifiers as well asfertilizers, micronutrient donors or other formulations for obtainingspecial effects.

Suitable carriers and adjuvants, e.g. for agricultural use, can be solidor liquid and are substances useful in formulation technology, e.g.natural or regenerated mineral substances, solvents, dispersants,wetting agents, tackifiers, thickeners, binders or fertilizers. Suchcarriers are for example described in WO 97/33890.

Suspension concentrates are aqueous formulations in which finely dividedsolid particles of the active compound are suspended. Such formulationsinclude anti-settling agents and dispersing agents and may furtherinclude a wetting agent to enhance activity as well an anti-foam and acrystal growth inhibitor. In use, these concentrates are diluted inwater and normally applied as a spray to the area to be treated. Theamount of active ingredient may range from 0.5% to 95% of theconcentrate.

Wettable powders are in the form of finely divided particles whichdisperse readily in water or other liquid carriers. The particlescontain the active ingredient retained in a solid matrix. Typical solidmatrices include fuller's earth, kaolin clays, silicas and other readilywet organic or inorganic solids. Wettable powders normally contain from5% to 95% of the active ingredient plus a small amount of wetting,dispersing or emulsifying agent.

Emulsifiable concentrates are homogeneous liquid compositionsdispersible in water or other liquid and may consist entirely of theactive compound with a liquid or solid emulsifying agent, or may alsocontain a liquid carrier, such as xylene, heavy aromatic naphthas,isophorone and other non-volatile organic solvents. In use, theseconcentrates are dispersed in water or other liquid and normally appliedas a spray to the area to be treated. The amount of active ingredientmay range from 0.5% to 95% of the concentrate.

Granular formulations include both extrudates and relatively coarseparticles and are usually applied without dilution to the area in whichtreatment is required. Typical carriers for granular formulationsinclude sand, fuller's earth, attapulgite clay, bentonite clays,montmorillonite clay, vermiculite, perlite, calcium carbonate, brick,pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corncobs, ground peanut hulls, sugars, sodium chloride, sodium sulphate,sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide,titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth,calcium sulphate and other organic or inorganic materials which absorbor which can be coated with the active compound. Granular formulationsnormally contain 5% to 25% of active ingredients which may includesurface-active agents such as heavy aromatic naphthas, kerosene andother petroleum fractions, or vegetable oils; and/or stickers such asdextrins, glue or synthetic resins.

Dusts are free-flowing admixtures of the active ingredient with finelydivided solids such as talc, clays, flours and other organic andinorganic solids which act as dispersants and carriers.

Microcapsules are typically droplets or granules of the activeingredient enclosed in an inert porous shell which allows escape of theenclosed material to the surroundings at controlled rates. Encapsulateddroplets are typically 1 to 50 microns in diameter. The enclosed liquidtypically constitutes 50 to 95% of the weight of the capsule and mayinclude solvent in addition to the active compound. Encapsulatedgranules are generally porous granules with porous membranes sealing thegranule pore openings, retaining the active species in liquid forminside the granule pores. Granules typically range from 1 millimetre to1 centimetre and preferably 1 to 2 millimetres in diameter. Granules areformed by extrusion, agglomeration or prilling, or are naturallyoccurring. Examples of such materials are vermiculite, sintered clay,kaolin, attapulgite clay, sawdust and granular carbon. Shell or membranematerials include natural and synthetic rubbers, cellulosic materials,styrene-butadiene copolymers, polyacrylonitriles, polyacrylates,polyesters, polyamides, polyureas, polyurethanes and starch xanthates.

Other useful formulations for agrochemical applications include simplesolutions of the active ingredient in a solvent in which it iscompletely soluble at the desired concentration, such as acetone,alkylated naphthalenes, xylene and other organic solvents. Pressurisedsprayers, wherein the active ingredient is dispersed in finely-dividedform as a result of vaporisation of a low boiling dispersant solventcarrier, may also be used.

Suitable agricultural adjuvants and carriers that are useful informulating the compositions of the invention in the formulation typesdescribed above are well known to those skilled in the art.

Liquid carriers that can be employed include, for example, water,toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethylketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone,amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol,alkyl acetates, diacetonalcohol, 1,2-dichloropropane, diethanolamine,p-diethylbenzene, diethylene glycol, diethylene glycol abietate,diethylene glycol butyl ether, diethylene glycol ethyl ether, diethyleneglycol methyl ether, N,N-dimethyl formamide, dimethyl sulfoxide,1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether,dipropylene glycol dibenzoate, diproxitol, alkyl pyrrolidinone, ethylacetate, 2-ethyl hexanol, ethylene carbonate, 1,1,1-trichloroethane,2-heptanone, alpha pinene, d-limonene, ethylene glycol, ethylene glycolbutyl ether, ethylene glycol methyl ether, gamma-butyrolactone,glycerol, glycerol diacetate, glycerol monoacetate, glycerol triacetate,hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate,isooctane, isophorone, isopropyl benzene, isopropyl myristate, lacticacid, laurylamine, mesityl oxide, methoxy-propanol, methyl isoamylketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyloleate, methylene chloride, m-xylene, n-hexane, n-octylamine,octadecanoic acid, octyl amine acetate, oleic acid, oleylamine,o-xylene, phenol, polyethylene glycol (PEG400), propionic acid,propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene,triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin,mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amylacetate, butyl acetate, methanol, ethanol, isopropanol, and highermolecular weight alcohols such as amyl alcohol, tetrahydrofurfurylalcohol, hexanol, octanol, etc., ethylene glycol, propylene glycol,glycerine and N-methyl-2-pyrrolidinone. Water is generally the carrierof choice for the dilution of concentrates.

Suitable solid carriers include, for example, talc, titanium dioxide,pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk,diatomaxeous earth, lime, calcium carbonate, bentonite clay, fuller'searth, cotton seed hulls, wheat flour, soybean flour, pumice, woodflour, walnut shell flour and lignin.

A broad range of surface-active agents are advantageously employed inboth said liquid and solid compositions, especially those designed to bediluted with carrier before application. These agents, when used,normally comprise from 0.1% to 15% by weight of the formulation. Theycan be anionic, cationic, non-ionic or polymeric in character and can beemployed as emulsifying agents, wetting agents, suspending agents or forother purposes. Typical surface active agents include salts of alkylsulfates, such as diethanolammonium lauryl sulphate; alkylarylsulfonatesalts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkyleneoxide addition products, such as nonylphenol-C.sub. 18 ethoxylate;alcohol-alkylene oxide addition products, such as tridecylalcohol-C.sub. 16 ethoxylate; soaps, such as sodium stearate;alkylnaphthalenesulfonate salts, such as sodiumdibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts,such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitol esters, such assorbitol oleate; quaternary amines, such as lauryl trimethylammoniumchloride; polyethylene glycol esters of fatty acids, such aspolyethylene glycol stearate; block copolymers of ethylene oxide andpropylene oxide; and salts of mono and dialkyl phosphate esters.

Other adjuvants commonly utilized in agricultural compositions includecrystallisation inhibitors, viscosity modifiers, suspending agents,spray droplet modifiers, pigments, antioxidants, foaming agents,anti-foaming agents, light-blocking agents, compatibilizing agents,antifoam agents, sequestering agents, neutralising agents and buffers,corrosion inhibitors, dyes, odorants, spreading agents, penetrationaids, micronutrients, emollients, lubricants and sticking agents.

In addition, further, other biocidally active ingredients orcompositions may be combined with the compositions of the invention andused in the methods of the invention and applied simultaneously orsequentially with the compositions of the invention. When appliedsimultaneously, these further active ingredients may be formulatedtogether with the compositions of the invention or mixed in, forexample, the spray tank. These further biocidally active ingredients maybe fungicides, herbicides, insecticides, bactericides, acaricides,nematicides and/or plant growth regulators.

In addition, the compositions of the invention may also be applied withone or more systemically acquired resistance inducers (“SAR” inducer).SAR inducers are known and described in, for example, U.S. Pat. No.6,919,298 and include, for example, salicylates and the commercial SARinducer acibenzolar-S-methyl.

The compounds of formula (I) are normally used in the form ofcompositions and can be applied to the crop area or plant to be treated,simultaneously or in succession with further compounds. These furthercompounds can be e.g. fertilizers or micronutrient donors or otherpreparations, which influence the growth of plants. They can also beselective herbicides or non-selective herbicides as well asinsecticides, fungicides, bactericides, nematicides, molluscicides ormixtures of several of these preparations, if desired together withfurther carriers, surfactants or application promoting adjuvantscustomarily employed in the art of formulation.

The compounds of formula (I) may be used in the form of (fungicidal)compositions for controlling or protecting against phytopathogenicmicroorganisms, comprising as active ingredient at least one compound offormula (I) or of at least one preferred individual compound asabove-defined, in free form or in agrochemically usable salt form, andat least one of the above-mentioned adjuvants.

The invention therefore provides a composition, preferably a fungicidalcomposition, comprising at least one compound formula (I) anagriculturally acceptable carrier and optionally an adjuvant. Anagricultural acceptable carrier is for example a carrier that issuitable for agricultural use. Agricultural carriers are well known inthe art. Preferably said composition may comprise at least one or morepesticidally active compounds, for example an additional fungicidalactive ingredient in addition to the compound of formula (I).

The compound of formula (I) may be the sole active ingredient of acomposition or it may be admixed with one or more additional activeingredients such as a pesticide, fungicide, synergist, herbicide orplant growth regulator where appropriate. An additional activeingredient may, in some cases, result in unexpected synergisticactivities.

Examples of suitable additional active ingredients include thefollowing: 1,2,4-thiadiazoles, 2,6-dinitroanilines, acylalanines,aliphatic nitrogenous compounds, amidines, aminopyrimidinols, anilides,anilino-pyrimidines, anthraquinones, antibiotics, aryl-phenylketones,benzamides, benzene-sulfonamides, benzimidazoles, benzothiazoles,benzothiodiazoles, benzothiophenes, benzoylpyridines, benzthiadiazoles,benzylcarbamates, butylamines, carbamates, carboxamides, carpropamids,chloronitriles, cinnamic acid amides, copper containing compounds,cyanoacetamideoximes, cyanoacrylates, cyanoimidazoles,cyanomethylene-thiazolidines, dicarbonitriles, dicarboxamides,dicarboximides, dimethylsulphamates, dinitrophenol carbonates,dinitrophenysl, dinitrophenyl crotonates, diphenyl phosphates, dithiinocompounds, dithiocarbamates, dithioethers, dithiolanes,ethyl-amino-thiazole carboxamides, ethyl-phosphonates, furancarboxamides, glucopyranoxyls, glucopyranoxyls, glutaronitriles,guanidines, herbicides/plant growth regulatosr, hexopyranosylantibiotics, hydroxy(2-amino)pyrimidines, hydroxyanilides,hydroxyisoxazoles, imidazoles, imidazolinones, insecticides/plant growthregulators, isobenzofuranones, isoxazolidinyl-pyridines, isoxazolines,maleimides, mandelic acid amides, mectin derivatives, morpholines,norpholines, n-phenyl carbamates, organotin compounds, oxathiincarboxamides, oxazoles, oxazolidine-diones, phenols, phenoxy quinolines,phenyl-acetamides, phenylamides, phenylbenzamides,phenyl-oxo-ethyl-thiophenes amides, phenylpyrroles, phenylureas,phosphorothiolates, phosphorus acids, phthalamic acids, phthalimides,picolinamides, piperazines, piperidines, plant extracts, polyoxins,propionamides, pthalimides, pyrazole-4-carboxamides, pyrazolinones,pyridazinones, pyridines, pyridine carboxamides, pyridinyl-ethylbenzamides, pyrimdinamines, pyrimidines, pyrimidine-amines,pyrimidione-hydrazone, pyrrolidines, pyrrolquinoliones, quinazolinones,quinolines, quinoline derivatives, quinoline-7-carboxylic acids,quinoxalines, spiroketalamines, strobilurins, sulfamoyl triazoles,sulphamides, tetrazolyloximes, thiadiazines, thiadiazole carboxamides,thiazole carboxanides, thiocyanates, thiophene carboxamides, toluamides,triazines, triazobenthiazoles, triazoles, triazole-thiones,triazolo-pyrimidylamine, valinamide carbamates, ammonium methylphosphonates, arsenic-containing compounds, benyimidazolylcarbamates,carbonitriles, carboxanilides, carboximidamides, carboxylicphenylamides, diphenyl pyridines, furanilides, hydrazine carboxamides,imidazoline acetates, isophthalates, isoxazolones, mercury salts,organomercury compounds, organophosphates, oxazolidinediones,pentylsulfonyl benzenes, phenyl benzamides, phosphonothionates,phosphorothioates, pyridyl carboxamides, pyridyl furfuryl ethers,pyridyl methyl ethers, SDHIs, thiadiazinanethiones, thiazolidines.

A further aspect of invention is related to a method of controlling orpreventing an infestation of plants, e.g. useful plants such as cropplants, propagation material thereof, e.g. seeds, harvested crops, e.g.harvested food crops, or of non-living materials by phytopathogenic orspoilage microorganisms or organisms potentially harmful to man,especially fungal organisms, which comprises the application of acompound of formula (I) or of a preferred individual compound asabove-defined as active ingredient to the plants, to parts of the plantsor to the locus thereof, to the propagation material thereof, or to anypart of the non-living materials.

Controlling or preventing means reducing infestation by insects or byphytopathogenic or spoilage microorganisms or organisms potentiallyharmful to man, especially fungal organisms, to such a level that animprovement is demonstrated.

A preferred method of controlling or preventing an infestation of cropplants by phytopathogenic microorganisms, especially fungal organisms,or insects which comprises the application of a compound of formula (I),or an agrochemical composition which contains at least one of saidcompounds, is foliar application. The frequency of application and therate of application will depend on the risk of infestation by thecorresponding pathogen or insect. However, the compounds of formula (I)can also penetrate the plant through the roots via the soil (systemicaction) by drenching the locus of the plant with a liquid formulation,or by applying the compounds in solid form to the soil, e.g. in granularform (soil application). In crops of water rice such granulates can beapplied to the flooded rice field. The compounds of formula (I) may alsobe applied to seeds (coating) by impregnating the seeds or tubers eitherwith a liquid formulation of the fungicide or coating them with a solidformulation.

A formulation, e.g. a composition containing the compound of formula(I), and, if desired, a solid or liquid adjuvant or monomers forencapsulating the compound of formula (I), may be prepared in a knownmanner, typically by intimately mixing and/or grinding the compound withextenders, for example solvents, solid carriers and, optionally, surfaceactive compounds (surfactants).

The application methods for the compositions, that is the methods ofcontrolling pests of the abovementioned type, such as spraying,atomizing, dusting, brushing on, dressing, scattering or pouring—whichare to be selected to suit the intended aims of the prevailingcircumstances—and the use of the compositions for controlling pests ofthe abovementioned type are other subjects of the invention. Typicalrates of concentration are between 0.1 and 1000 ppm, preferably between0.1 and 500 ppm, of active ingredient. The rate of application perhectare is preferably 1 g to 2000 g of active ingredient per hectare,more preferably 10 to 1000 g/ha, most preferably 10 to 600 g/ha. Whenused as seed drenching agent, convenient dosages are from 10mg to 1 g ofactive substance per kg of seeds.

When the combinations of the present invention are used for treatingseed, rates of 0.001 to 50 g of a compound of formula (I) per kg ofseed, preferably from 0.01 to 10 g per kg of seed are generallysufficient.

Suitably, a composition comprising a compound of formula (I) accordingto the present invention is applied either preventative, meaning priorto disease development or curative, meaning after disease development.

The compositions of the invention may be employed in any conventionalform, for example in the form of a twin pack, a powder for dry seedtreatment (DS), an emulsion for seed treatment (ES), a flowableconcentrate for seed treatment (FS), a solution for seed treatment (LS),a water dispersible powder for seed treatment (WS), a capsule suspensionfor seed treatment (CF), a gel for seed treatment (GF), an emulsionconcentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE),a capsule suspension (CS), a water dispersible granule (WG), anemulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion,oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oilmiscible flowable (OF), an oil miscible liquid (OL), a solubleconcentrate (SL), an ultra-low volume suspension (SU), an ultra-lowvolume liquid (UL), a technical concentrate (TK), a dispersibleconcentrate (DC), a wettable powder (WP) or any technically feasibleformulation in combination with agriculturally acceptable adjuvants.

Such compositions may be produced in conventional manner, e.g. by mixingthe active ingredients with appropriate formulation inerts (diluents,solvents, fillers and optionally other formulating ingredients such assurfactants, biocides, anti-freeze, stickers, thickeners and compoundsthat provide adjuvancy effects). Also conventional slow releaseformulations may be employed where long lasting efficacy is intended.Particularly formulations to be applied in spraying forms, such as waterdispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like),wettable powders and granules, may contain surfactants such as wettingand dispersing agents and other compounds that provide adjuvancyeffects, e.g. the ondensation product of formaldehyde with naphthalenesulphonate, an alkylarylsulphonate, a lignin sulphonate, a fatty alkylsulphate, and ethoxylated alkylphenol and an ethoxylated fatty alcohol.

A seed dressing formulation is applied in a manner known per se to theseeds employing the combination of the invention and a diluent insuitable seed dressing formulation form, e.g. as an aqueous suspensionor in a dry powder form having good adherence to the seeds. Such seeddressing formulations are known in the art. Seed dressing formulationsmay contain the single active ingredients or the combination of activeingredients in encapsulated form, e.g. as slow release capsules ormicrocapsules.

In general, the formulations include from 0.01 to 90% by weight ofactive agent, from 0 to 20% agriculturally acceptable surfactant and 10to 99.99% solid or liquid formulation inerts and adjuvant(s), the activeagent consisting of at least the compound of formula (I) together withcomponent (B) and (C), and optionally other active agents, particularlymicrobiocides or conservatives or the like. Concentrated forms ofcompositions generally contain in between about 2 and 80%, preferablybetween about 5 and 70% by weight of active agent. Application forms offormulation may for example contain from 0.01 to 20% by weight,preferably from 0.01 to 5% by weight of active agent. Whereas commercialproducts will preferably be formulated as concentrates, the end userwill normally employ diluted formulations.

Whereas it is preferred to formulate commercial products asconcentrates, the end user will normally use dilute formulations.

EXAMPLES

The Examples which follow serve to illustrate the invention. Certaincompounds of the invention can be distinguished from known compounds byvirtue of greater efficacy at low application rates, which can beverified by the person skilled in the art using the experimentalprocedures outlined in the Examples, using lower application rates ifnecessary, for example 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppmor 0.2 ppm.

Throughout this description, temperatures are given in degrees Celsiusand “m.p.” means melting point. LC/MS means Liquid Chromatography MassSpectroscopy and the description of the apparatus and the methods are:

Method G:

Spectra were recorded on a Mass Spectrometer from Waters (SQD, SODIISingle quadrupole mass spectrometer) equipped with an electrospraysource (Polarity: positive and negative ions), Capillary: 3.00 kV, Conerange: 30 V, Extractor: 2.00 V, Source Temperature: 150° C., DesolvationTemperature: 350° C., Cone Gas Flow: 50 l/h, Desolvation Gas Flow: 650l/h, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binarypump, heated column compartment, diode-array detector and ELSD detector.Column: Waters UPLC HSS T3 , 1.8 μm, 30×2.1 mm, Temp: 60° C., DADWavelength range (nm): 210 to 500, Solvent Gradient: A=water+5%MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH, gradient: 10-100% B in 1.2min; Flow (ml/min) 0.85

Method H:

Spectra were recorded on a Mass Spectrometer from Waters (SQD, SODIISingle quadrupole mass spectrometer) equipped with an electrospraysource (Polarity: positive and negative ions), Capillary: 3.00 kV, Conerange: 30V, Extractor: 2.00 V, Source Temperature: 150° C., DesolvationTemperature: 350° C., Cone Gas Flow: 50 l/h, Desolvation Gas Flow: 650l/h, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binarypump, heated column compartment, diode-array detector and ELSD detector.Column: Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, Temp: 60° C., DADWavelength range (nm): 210 to 500, Solvent Gradient: A=water+5%MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH, 20 gradient: 10-100% B in2.7 min; Flow (ml/min) 0.85

Method W:

Spectra were recorded on a Mass Spectrometer (ACQUITY UPLC) from Waters(SQD, SODII Single quadrupole mass spectrometer) equipped with anelectrospray source (Polarity: positive or negative ions, Capillary: 3.0kV, Cone: 30V, Extractor: 3.00 V, Source Temperature: 150° C.,Desolvation Temperature: 400° C., Cone Gas Flow: 60 L/Hr, DesolvationGas Flow: 700 L/Hr, Mass range: 140 to 800 Da), DAD Wavelength range(nm): 210 to 400, and an Acquity UPLC from Waters: Solvent degasser,binary pump, heated column compartment and diode-array detector. Column:Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, Temp: 60° C., DAD Wavelengthrange (nm): 210 to 500, Solvent Gradient: A=Water/Methanol 9:1,0.1%formic acid, B=Acetonitrile+0.1% formic acid, gradient: 0-100% B in 2.5min; Flow (ml/min) 0.75

FORMULATION EXAMPLES

Wettable powders a) b) c) active ingredient [compound of formula (I)]25%  50% 75% sodium lignosulfonate 5%  5% — sodium lauryl sulfate 3% — 5% sodium diisobutylnaphthalenesulfonate —  6% 10% phenol polyethyleneglycol ether —  2% — (7-8 mol of ethylene oxide) highly dispersedsilicic acid 5% 10% 10% Kaolin 62%  27% —

The active ingredient is thoroughly mixed with the adjuvants and themixture is thoroughly ground in a suitable mill, affording wettablepowders that can be diluted with water to give suspensions of thedesired concentration.

Powders for dry seed treatment a) b) c) active ingredient [compound offormula (I)] 25% 50% 75% light mineral oil  5%  5%  5% highly dispersedsilicic acid  5%  5% — Kaolin 65% 40% — Talcum — 20

The active ingredient is thoroughly mixed with the adjuvants and themixture is thoroughly ground in a suitable mill, affording powders thatcan be used directly for seed treatment.

Emulsifiable concentrate active ingredient [compound of formula (I)] 10%octylphenol polyethylene glycol ether  3% (4-5 mol of ethylene oxide)calcium dodecylbenzenesulfonate  3% castor oil polyglycol ether (35 molof ethylene oxide)  4% Cyclohexanone 30% xylene mixture 50%

Emulsions of any required dilution, which can be used in plantprotection, can be obtained from this concentrate by dilution withwater.

Dusts a) b) c) Active ingredient [compound of formula (I)]  5%  6%  4%talcum 95% — — Kaolin — 94% — mineral filler — — 96%

Ready-for-use dusts are obtained by mixing the active ingredient withthe carrier and grinding the mixture in a suitable mill. Such powderscan also be used for dry dressings for seed.

Extruder granules Active ingredient [compound of formula (I)] 15% sodiumlignosulfonate  2% carboxymethylcellulose  1% Kaolin 82%

The active ingredient is mixed and ground with the adjuvants, and themixture is moistened with water. The mixture is extruded and then driedin a stream of air.

Coated granules Active ingredient [compound of formula (I)] 8%polyethylene glycol (mol. wt. 200) 3% Kaolin 89% 

The finely ground active ingredient is uniformly applied, in a mixer, tothe kaolin moistened with polyethylene glycol. Non-dusty coated granulesare obtained in this manner.

Suspension concentrate active ingredient [compound of formula (I)] 40%propylene glycol 10% nonylphenol polyethylene glycol ether (15 mol ofethylene oxide)  6% Sodium lignosulfonate 10% carboxymethylcellulose  1%silicone oil (in the form of a 75% emulsion in water)  1% Water 32%

The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired dilution can be obtained by dilution with water. Using suchdilutions, living plants as well as plant propagation material can betreated and protected against infestation by microorganisms, byspraying, pouring or immersion.

Flowable concentrate for seed treatment active ingredient [compound offormula (I)] 40%  propylene glycol 5% copolymer butanol PO/EO 2%tristyrenephenole with 10-20 moles EO 2% 1,2-benzisothiazolin-3-one (inthe form of a 0.5%   20% solution in water) monoazo-pigment calcium salt5% Silicone oil (in the form of a 75% emulsion in water) 0.2%   Water45.3%  

The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired dilution can be obtained by dilution with water. Using suchdilutions, living plants as well as plant propagation material can betreated and protected against infestation by microorganisms, byspraying, pouring or immersion.

Slow Release Capsule Suspension

28 parts of a combination of the compound of formula (I) are mixed with2 parts of an aromatic solvent and 7 parts of toluenediisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). Thismixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol,0.05 parts of a defoamer and 51.6 parts of water until the desiredparticle size is achieved. To this emulsion a mixture of 2.8 parts1,6-diaminohexane in 5.3 parts of water is added. The mixture isagitated until the polymerization reaction is completed.

The obtained capsule suspension is stabilized by adding 0.25 parts of athickener and 3 parts of a dispersing agent. The capsule suspensionformulation contains 28% of the active ingredients. The medium capsulediameter is 8-15 microns.

The resulting formulation is applied to seeds as an aqueous suspensionin an apparatus suitable for that purpose.

PREPARATION EXAMPLES Example 1 Preparation ofN-(1-benzyl-1,3-dimethyl-butyl)quinoline-3-carboxamide Step 1:preparation of 2,4-dimethyl-1-phenyl-pentan-2-ol

A solution of 4-methyl-2-pentanone (3.0 g, 29.4 mmol) in diethyl ether(25 mL) was added drop wise to benzyl magnesium chloride intetrahydrofuran (2 M in tetrahydrofuran, 22 mL, 44 mmol) at RT. Thereaction mixture was then warmed to 35° C. and aged for 3 h at thistemperature. After cooling to RT, aqueous HCl (2 M) was added to thereaction and the mixture was portioned between water and ethyl acetate.The organic layer was washed with brine, dried over Na₂SO₄, filtratedand concentrated in vacuo. The residue was purified by chromatography onsilica gel to afford the title compound as colorless liquid.

¹H NMR (400 MHz, CDCl₃) δ 7.18-7.34 (m, 5H), 2.65-2.85 (m, 2H),1.81-1.99 (m, 1H), 1.42 (dd, 2H), 1.15 (s, 3H), 0.98 (dd, 6H).

Step 2: preparation ofN-(1-benzyl-1,3-dimethyl-butyl)-2-chloro-acetamide

To a solution of 2,4-dimethyl-1-phenyl-pentan-2-ol (3.6 g, 19 mmol) andchloroacetonitrile (2.4 mL, 37 mmol) in acetic acid (11 mL) cooled to0-5° C. was added drop wise concentrated sulfuric acid (3.1 mL, 56mmol). The resulting slurry was warmed to 20° C. and stirred for 3 h atthis temperature. The reaction mixture was then diluted with water andextracted with ethyl acetate. The organic layer was washed with aqueousNaHCO₃, brine, dried over MgSO₄, filtrated and concentrated in vacuo.The residue was purified by chromatography on silica gel to afford thetitle compound as colorless solid.

¹H NMR (400 MHz, CDCl₃) δ 7.20-7.34 (m, 3H), 7.08-7.16 (m, 2H), 6.13(br. s., 1H), 3.94 (s, 2H), 3.21 (d, 1H), 2.90 (d, 1H), 1.86-1.95 (m, 1H), 1.73-1.86 (m, 1H), 1.54 (dd, 1H), 1.31 (s, 3H), 0.96 (dd, 6H).

Step 3: preparation of 2,4-dimethyl-1-phenyl-pentan-2-amine

A solution of N-(1-benzyl-1,3-dimethyl-butyl)-2-chloro-acetamide (3.0 g,11.2 mmol), acetic acid (3.9 mL, 67 mmol) and thiourea (1.02 g, 13.4mmol) in ethanol (30 mL) was warmed to 80° C. and stirred for 18 h atthis temperature. The reaction mixture was then cooled to 20° C.,diluted with aqueous HCl (0.5 M) filtrated through a short pad ofCelite. The filtrate was washed with ethyl acetate; the aqueous layerwas then basified with 4 M NaOH and extracted with n-hexanes. Then-hexanes layer was washed with brine, dried over Na₂SO₄, filtrated andconcentrated in vacuo to afford the title compound as light brown oil.

¹H NMR (400 MHz, CDCl₃) δ 7.14-7.34 (m, 5H), 2.59-2.71 (m, 2H),1.78-1.94 (m, 1H), 1.26-1.41 (m, 2H), 1.05 (s, 3H), 1.03 (br.s, 2H),0.98 (dd, 6H).

Step 4: preparation ofN-(1-benzyl-1,3-dimethyl-butyl)quinoline-3-carboxamide

To a solution of quinoline-3-carboxylic acid (0.20 g, 1.15 mmol),2,4-dimethyl-1-phenyl-pentan-2-amine (0.22 g, 1.15 mmol), triethylamine(0.14 g, 1.4 mmol) and 1-hydroxy-7-azabenzotriazole (0.16 g, 1.15 mmol)in dry dimethylformamide (5 mL) was addedN-(3-dimethylaminopropyl)-N′-ethylcarbodiimide HCl (0.22 g, 1.15 mmol)at RT and the resulting solution was aged for 18 h at 20° C. Water wasadded and the mixture was extracted with ethyl acetate. The organicphase was washed with brine, dried over Na₂SO₄, filtrated andconcentrated in vacuo. The residue was purified by chromatography onsilica gel to afford the title compound as white solid, m.p. 121° C.

¹H NMR (400 MHz, CDCl₃) δ 9.12 (d, 1H), 8.40 (d, 1 H), 8.13 (d, 1H),7.86 (d, 1 H), 7.74-7.82 (m, 1H), 7.56-7.64 (m, 1H), 7.16-7.30 (m, 5H),5.73 (s, 1H), 3.46 (d, 1H), 2.98 (d, 1H), 2.17 (dd, 1H), 1.84-1.99 (m,1H), 1.67 (dd, 1H), 1.43 (s, 3H), 1.02 (d, 6H).

Example 2 Preparation ofN-(1-benzyl-1,3-dimethyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamideStep 1: preparation of2-methyl-N-(1-methyl-2-phenyl-ethylidene)propane-2-sulfinamide

1-Phenylpropan-2-one (8.30 g,61.9 mmol) was dissolved in tetrahydrofuran(75 mL), titanium(IV)ethoxide (32.6 g, 92.8 mmol) and2-methylpropane-2-sulfinamide (7.50 g, 61.9 mmol) was added sequentiallyat room temperature and the resulting mixture was warmed to 60° C. Afterstirring for 2 h at 60° C., the reaction was cooled to room temperatureand quenched with aqueous NaHCO₃. The resulting mixture was filtratedand the filter cake was washed with ethyl acetate. The combinedfiltrates were extracted with ethyl acetate, the organic layer waswashed with brine, dried over sodium sulfate, filtrated and concentratedin vacuo to afford the title compound as light yellow oil (purity>80%,ca. 4:1 ratio of cis-trans isomers) which was used as such for the nextstep.

¹H NMR (400 MHz, CDCl₃, major isomer) δ 7.17-7.43 (m, 5H), 3.72 (d, 1H),3.70 (d, 1H), 2.32 (s, 3H), 1.23 (s, 9H)

Step 2: preparation ofN-(1-benzyl-1,3-dimethyl-but-3-enyI)-2-methyl-propane-2-sulfinamide

A solution of crude2-methyl-N-(1-methyl-2-phenyl-ethylidene)propane-2-sulfinamide (80%purity, 7.4 g, 24.9 mmol) in dichloromethane (100 mL) was added slowlyto a commercially available solution of 2-methylallylmagnesium chloridein THF (0.5 M, 75 mL, 37.4 mmol) maintained at −50° C. The reactionmixture was gradually warmed to 20° C. over 4 h and stirred overnight at20° C. Saturated NH₄Cl solution was then added, the mixture wasextracted with ethyl acetate and the organic layer was washed withbrine, dried over sodium sulfate, filtrated and concentrated in vacuo.The residue was purified by flash chromatography on silica gel to affordthe title compound as mixture diastereoisomers.

¹H NMR (400 MHz, CDCl₃, major isomer) δ 6.94-7.18 (m, 5H), 4.82 (s, 1H),4.71 (s, 1H), 3.39 (s, 1H), 2.76 (d, 1H), 2.55 (d, 1H), 2.21 (d, 2H),1.63 (s, 3H), 1.06 (s, 3H), 0.94 (s, 9H).

Step 3: preparation ofN-(1-benzyl-1,3-dimethyl-but-3-enyI)-8-fluoro-quinoline-3-carboxamide

To an ice cold solution ofN-(1-benzyl-1,3-dimethyl-but-3-enyI)-2-methyl-propane-2-sulfinamide (5.2g, 15.9 mmol) in methanol (16 mL) was added HCl in 1,4-dioxane (4 M, 6mL, 24 mmol) and the resulting solution was stirred for 2 h at 0-5° C.All volatiles were then removed in vacuo to afford a brown, gummyresidue which was triturated with a mixture of diethyl ether/heptanes.The resulting light brown solid was dried in vacuo and used as such forthe next step.

A part of the solid hydrochloride salt obtained above (2 g, 8.0 mmol)was suspended in dichloromethane (40 mL) and8-fluoroquinoline-3-carboxylic acid (1.68 g, 8.8 mmol), triethylamine(2.8 mL, 19.9 mmol), 1-hydroxy-7-azabenzotriazol (1.2 g, 8.8 mmol) andN-(3-dimethylaminopropyl)-N′-ethylcarbodiimide-HCl (1.72 g, 8.8 mmol)was added sequentially at ambient temperature. The resulting mixture wasaged for 2 h at 20° C. Water was then added and the mixture wasextracted with dichloromethane. The organic layer was washed with brine,dried over sodium sulfate, filtrated and concentrated in vacuo. Theresidue was purified by flash chromatography on silica gel to afford thetitle compound as white solid, m.p. 115-117° C.

¹H NMR (400 MHz, CDCl₃) δ 9.11-9.26 (m, 1H), 8.50 (s, 1H), 7.72 (d, 1H),7.45-7.64 (m, 2H), 7.19-7.37 (m, 5H), 5.96 (s, 1H), 5.01 (s, 1H), 4.84(s, 1H), 3.57 (d, 1H), 3.08 (dd, 2H), 2.46 (d, 1H), 1.89 (s, 3H), 1.47(s, 3H).

¹⁹F NMR (377 MHz, CDCl₃) δ −124.64 (s).

Example 3N-(1-benzyl-3,3,3-trifluoro-1-methyl-propyl)-7,8-difluoro-quinoline-3-carboxamideStep 1: preparation of ethyl 2-benzyl-4,4,4-trifluoro-2-methyl-butanoate

n-Butyl lithium (2.5 M in hexanes, 100 mL, 248.9 mmol) was added slowlyto a solution of diisopropyl amine (35.2 mL, 248.9 mmol) intetrahydrofuran (400 mL) at −70° C. The resulting solution was aged for30 min at −70° C. and then ethyl 4,4,4-trifluorobutyrate (36 g, 207.4mmol) was added drop wise. The reaction was stirred for 2 h at −70° C.,benzyl bromide (43.2 g, 248.9 mmol) was added and the reaction mixturewas gradually warmed to room temperature over ca. 2 h. Saturated NH₄Clsolution was added and the mixture was extracted with methyl tertbutylether. The organic layer was washed with water, brine, dried over MgSO₄,filtrated and concentrated in vacuo. The residual oil was passed througha short pad of silica gel, the pad was rinsed with cyclohexane:ethylacetate (2:1) and the filtrate was concentrated in vacuo, affordingethyl 4,4,4-trifluoro-2-methyl-butanoate as light orange oil.

n-Butyl lithium (2.5 M in hexanes, 99 mL, 247.2 mmol) was added slowlyto a solution of diisopropyl amine (35 mL, 247.2 mmol) intetrahydrofuran (380 mL) at −70° C. The resulting solution was aged for30 min at −70° C. and then the crude product obtained above (49.5 g,190.2 mmol, diluted with tetrahydrofuran (30 mL)) was added slowly at−70° C. The resulting dark solution was stirred for 2 h at −70° C.before methyl iodide (13.1 mL, 209.3 mmol) was added. The reactionmixture was gradually warmed to 20° C. over ca. 3 h, then quenched withsaturated NH₄Cl solution and extracted with methyl tertbutylether. Theorganic layer was washed with water, brine, dried over MgSO₄, filtratedand concentrated in vacuo. The residual oil was passed through a shortpad of silica gel, the pad was rinsed with cyclohexane:ethyl acetate(2:1) and the filtrate was concentrated in vacuo, affording the titlecompound as light brown oil (ca. 80% pure).

¹H NMR (400 MHz, CDCl₃) δ 7.05-7.33 (m, 5H), 4.13 (q, 2H), 2.98 (d, 1H),2.81-2.72 (m, 2H), 2.11-2.32 (m, 1H), 1.28 (s, 3H), 1.21 (t, 3H).

Step 2: preparation of 2-benzyl-4,4,4-trifluoro-2-methyl-butanamide

A solution of ethyl 2-benzyl-4,4,4-trifluoro-2-methyl-butanoate (25.5 g,93.0 mmol) in 1,4-dioxane (45 mL)/ethanol (45 mL) was treated with NaOH(7.6 g, 186 mmol) at room temperature, the resulting solution was warmedto 90° C. and aged for 1 h at 90° C. After cooling to room temperature,the reaction mixture was concentrated to about 50% of the originalvolume. The residue was diluted with water and washed with cyclohexane.The water layer was then acidified with HCl (conc.) under ice cooling attemp <25° C. and the mixture was extracted with DCM. The organic layerwere washed with brine, dried with Na₂SO₄, filtrated and concentrated invacuo to afford 2-benzyl-4,4,4-trifluoro-2-methyl-butanoic acid as darkyellow oil.

To a solution of crude 2-benzyl-4,4,4-trifluoro-2-methyl-butanoic acid(6.7 g, 27.2 mmol) and dimethyl formamide (0.1 mL, 1.4 mmol) indichloromethane (25 mL) was slowly added oxalyl chloride (2.5 mL, 28.6mmol) at 20° C. The resulting solution was stirred for 1 h at 20° C. andthen all volatiles were removed in vacuo. The residue was dissolved indichloromethane (25 mL) and the resulting solution was slowly added toice cooled, rapidly stirred aqueous ammonia solution (25-wt %, 21 mL).The resulting mixture was gradually warmed to room temperature andstirred for 30 min. Water was then added and the mixture was extracteddichloromethane. The organic layer was washed with water, brine, driedwith Na₂SO₄, filtrated and concentrated in vacuo to afford the titlecompound as light brown oil.

¹H NMR (400 MHz, CDCl₃) δ 7.13-7.44 (m, 5H), 5.42 (br s, 2H), 3.13 (d,1H), 2.97-3.09 (m, 1H), 2.67 (d, 1H), 2.18 (qd, 1H), 1.33 (s, 3H).

Step 3: preparation of 4,4,4-trifluoro-2-methyl-1-phenyl-butan-2-amine

To a solution of 2-benzyl-4,4,4-trifluoro-2-methyl-butanamide (6.6 g,26.9 mmol) in acetonitrile (25 mL)/water (25 mL) was addeddiacetoxyiodobenzene (9.73 g, 29.6 mmol) and trifluoroacetic acid (4.6mL, 59.2 mmol) at room temperature and the resulting mixture was stirredfor 18 h at room temperature. Acetonitrile was then removed in vacuo,the remaining aqueous emulsion was adjusted to pH1 with concentrated HCland washed with methyl tertbutylether. The aqueous layer was basified topH12 with NaOH (8 M) and extracted with methyl tertbutylether. Theorganic layer was washed with brine, dried over Na₂SO₄, filtrated andconcentrated in vacuo to afford the title compound as yellow oil.

¹H NMR (400 MHz, CDCl₃) δ 7.16-7.50 (m, 5H), 2.81 (s, 2H), 2.13-2.41 (m,2H), 1.28 (s, 3H).

Step 4: preparation ofN-(1-benzyl-3,3,3-trifluoro-1-methyl-propyl)-7,8-difluoro-quinoline-3-carboxamide

To a solution of 7,8-difluoroquinoline-3-carboxylic acid (0.35 g, 1.67mmol), 4,4,4-trifluoro-2-methyl-1-phenyl-butan-2-amine (0.40 g, 0.84mmol), triethylamine (0.6 mL, 4.2 mmol) and 1-hydroxy-7-azabenzotriazol(0.27 g, 2.0 mmol) in dichloromethane (10 mL) was addedN-(3-dimethylaminopropyl)-N′-ethylcarbodiimide-HCl (0.39 g, 2.0 mmol) atroom temperature. The resulting mixture was stirred for 15 h at roomtemperature and then quenched with water. The mixture was extracted withdichloromethane, the organic layer was washed with water, brine, driedover Na₂SO₄, filtrated and concentrated in vacuo. The residue waspurified by flash chromatography on silica gel to afford the titlecompound as white solid, m.p. 158-160° C.

¹H NMR (400 MHz, CDCl₃) δ 9.07 (d, 1H), 8.38 (t, 1H), 7.62 (ddd, 1H),7.47 (dt, 1H), 7.11-7.38 (m, 5H), 6.14 (s, 1H), 3.62 (d, 1H), 3.46 (dd,1H), 2.96 (d, 1H), 2.58 (qd, 1H), 1.50 (s, 3H)

¹⁹F NMR (377 MHz, CDCl₃) δ −59.75 (s, 1F), −132.03 (d, 1F), −150.23 (d,1F).

Example 4 Preparation of the Single Isomers:

-   N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-7,8-difluoro-quinoline-3-carboxamide    and-   N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-7,8-difluoro-quinoline-3-carboxamide

The racemicN-(1-benzyl-3,3,3-trifluoro-1-methyl-propyl)-7,8-difluoro-quinoline-3-carboxamidemixture was submitted to chiral resolution by preparative HPLCchromathography using the conditions outlined hereafter.

Analytical HPLC Method

-   SFC:Waters Acquity UPC²/QDa-   PDA Detector Waters Acquity UPC²-   Column: Daicel SFC CHIRALPAK® OZ, 3 μm, 0.3 cm×10 cm, 40° C. Mobile    phase: A: CO₂ B:-   iPr gradient: 10% B in 2.8 min-   ABPR: 1800 psi-   Flow rate: 2.0 ml/min-   Detection: 233 nm-   Sample concentration: 1 mg/mL in ACN/iPr 50/50-   Injection: 1 μL

Preparative HPLC Method:

-   Autopurification System from Waters: 2767 sample Manager, 2489    UV/Visible Detector, 2545 Quaternary Gradient Module.-   Column: Daicel CHIRALPAK® IF, 5 μm, 1.0 cm×25 cm-   Mobile phase: TBME/EtOH 98/02-   Flow rate: 10 ml/minDetection: UV 265 nm-   Sample concentration: 165 mg/mL in EE/ACN-   Injection: 30-90 μl, 5-15 mg

Results:

First eluting enantiomer Second eluting enantiomer Retention time (min)~1.05 Retention time (min) ~1.51 Chemical purity (area % at Chemicalpurity (area % at 220 nm) 99 220 nm) 99 Enantiomeric excess (%) >99Enantiomeric excess (%) >99

The compound with the elution time of 1.05 minute isN-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-7,8-difluoro-quinoline-3-carboxamide,corresponding to compound F-38.

The compound with the elution time of 1.51 minutes isN-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-7,8-difluoro-quinoline-3-carboxamide,corresponding to compound F-37.

Example 5 Preparation of the Single Isomers:

-   N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide-   N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide

The racemicN-(1-benzyl-3,3,3-trifluoro-1-methyl-propyl)-8-fluoro-quinoline-3-carboxamidemixture was submitted to chiral resolution by preparative HPLCchromathography using the conditions outlined hereafter.

Analytical HPLC Method

-   SFC:Waters Acquity UPC²/QDa-   PDA Detector Waters Acquity UPC²-   Column: Daicel SFC CHIRALPAK® ID, 3 μm, 0.3 cm×10 cm, 40° C.-   Mobile phase: A: CO2 B: iPr gradient: 15% B in 2.8 min-   ABPR: 1800 psi-   Flow rate: 2.0 ml/min-   Detection: 235 nm-   Sample concentration: 1 mg/mL in ACN/iPr 50/50-   Injection: 1 μL

Preparative HPLC Method:

-   Autopurification System from Waters: 2767 sample Manager, 2489    UV/Visible Detector, 2545 Quaternary Gradient Module.-   Column: Daicel CHIRALPAK® IF, 5 μm, 1.0 cm×25 cm-   Mobile phase: Hept/EtOH 95/05-   Flow rate: 10 ml/min-   Detection: UV 265 nm-   Sample concentration: 10 mg/mL in MeOH/DCM (1/1)-   Injection: 500 μl

Results:

First eluting enantiomer Second eluting enantiomer Retention time (min)~1.49 Retention time (min) ~1.88 Chemical purity (area % at Chemicalpurity (area % at 235 nm) 99 235 nm) 99 Enantiomeric excess (%) >99Enantiomeric excess (%) >99

The compound with the elution time of 1.49 minute isN-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide,corresponding to compound F-11. The compound with the elution time of1.88 minutes isN-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide,corresponding to compound F-12.

Example 6 Preparation of the Single Isomers:

-   N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide    and-   N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide

The racemicN-(1-benzyl-1,3-dimethyl-butyl)-8-fluoro-quinoline-3-carboxamide mixturewas submitted to chiral resolution by preparative HPLC chromathographyusing the conditions outlined hereafter.

Analytical HPLC Method:

-   SFC:Waters Acquity UPC²/QDa-   PDA Detector Waters Acquity UPC²-   Column: Daicel SFC CHIRALPAK® IA, 3 μm, 0.3 cm×10 cm, 40° C.-   Mobile phase: A: CO2 B: MeOH gradient: 25% B in 1.8 min-   ABPR: 1800 psi-   Flow rate: 2.0 ml/min-   Detection: 240 nm-   Sample concentration: 1 mg/mL in Hept/EtOH 90/10-   Injection: 3 μL

Preparative HPLC Method:

-   Autopurification System from Waters: 2767 sample Manager, 2489    UV/Visible Detector, 2545 Quaternary Gradient Module.-   Column: Daicel CHIRALPAK® IE, 5 μm, 1.0 cm×25 cm-   Mobile phase: Hept/EtOH 90/10-   Flow rate: 10 ml/min-   Detection: UV 265 nm-   Sample concentration: 100 mg/mL in MeOH/DCM (1/3) (filtered)-   Injection: 150 μl-250 μl

First eluting enantiomer Second eluting enantiomer Retention time (min)~0.97 Retention time (min) ~1.32 Chemical purity (area % at Chemicalpurity (area % at 240 nm) 99 240 nm) 99 Enantiomeric excess (%) >99Enantiomeric excess (%) >99

The compound with the elution time of 0.97 minute isN-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide,corresponding to compound F-1.

The compound with the elution time of 1.88 minutes isN-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide,corresponding to compound F-2.

Example 7 Preparation of the Single Isomers:

-   N-[(1R)-1-benzyl-3-fluoro-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide    and-   N-[(1S)-1-benzyl-3-fluoro-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide

The racemicN-(1-benzyl-3-fluoro-1,3-dimethyl-butyl)-8-fluoro-quinoline-3-carboxamidemixture was submitted to chiral resolution by preparative HPLCchromathography using the conditions outlined hereafter.

Analytical HPLC Method:

-   SFC:Waters Acquity UPC²/QDa-   PDA Detector Waters Acquity UPC²-   Column: Daicel SFC CHIRALPAK® IA, 3 μm, 0.3 cm×10 cm, 40° C.-   Mobile phase: A: CO2 B: MeOH gradient: 30% B in 1.8 min-   ABPR: 1800 psi-   Flow rate: 2.0 ml/min-   Detection: 230 nm-   Sample concentration: 1 mg/mL in ACN/iPr 50/50-   Injection: 1 μL

Preparative HPLC Method:

-   Autopurification System from Waters: 2767 sample Manager, 2489    UV/Visible Detector, 2545 Quaternary Gradient Module.-   Column: Daicel CHIRALPAK® IA, 5 μm, 1.0 cm×25 cm-   Mobile phase: Hept/EtOH 90/10-   Flow rate: 10 ml/min-   Detection: UV 265 nm-   Sample concentration: 127 mg/mL in EE-   Injection: 40-160 μl, 5-20 mg

First eluting enantiomer Second eluting enantiomer Retention time (min)~0.88 Retention time (min) ~1.51 Chemical purity (area % at Chemicalpurity (area % at 235 nm) 99 235 nm) 99 Enantiomeric excess (%) >99Enantiomeric excess (%) >99

The compound with the elution time of 0.88 minute isN-[(1R)-1-benzyl-3-fluoro-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide,corresponding to compound F-23.

The compound with the elution time of 1.51 minutes isN-[(1S)-1-benzyl-3-fluoro-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide,corresponding to compound F-24.

TABLE E Physical data of compounds of formula (I) RT [M + H] No. IUPACname STRUCTURE (min) measured Method MP° C. E-1 N-[2-(2- fluorophenyl)-1,1,2-trimethyl- propyl]quinoline- 3-carboxamide

1.08 351 G E-2 N-[2-(2- fluorophenyl)- 1,1-dimethyl- ethyl]quinoline-3-carboxamide

1.00 323 G E-3 N-[1,1-dimethyl- 2-[2- (trifluoromethoxy) phenyl]ethyl]quinoline-3- carboxamide

1.79 389 G   145- 149 E-4 N-[1-cyano-2-(2- fluorophenyl)-1- methyl-ethyl]quinoline- 3-carboxamide

1.35 334 G   134- 139 E-5 N-(1-benzyl-1,2- dimethyl- propyl)-8-fluoro-quinoline-3- carboxamide

1.12 351 G E-6 N-(1-benzyl-1,3- dimethyl-butyl)- 8-fluoro- quinoline-3-carboxamide

1.17 365 H   110- 112 E-7 N-[2-(4- chlorophenyl)-1- cyano-1-methyl-ethyl]-8-fluoro- quinoline-3- carboxamide

1.51 368 W E-8 N-[1-cyano-2- (2,4- difluorophenyl)- 1-methyl-ethyl]-8-fluoro- quinoline-3- carboxamide

1.43 370 W E-9 8-fluoro-N-[2-(2- methoxyphenyl)- 1,1-dimethyl-ethyl]quinoline- 3-carboxamide

1.64 353 W E-10 N-(1-cyano-1- methyl-2- phenyl-ethyl)-8-fluoro-quinoline- 3-carboxamide

1.37 334 W E-11 N-(1,1-dimethyl- 2-phenyl-ethyl)- 8-fluoro- quinoline-3-carboxamide

1.56 323 W E-12 N-(1-benzyl-2,2- dimethyl- propyl)-8-fluoro-quinoline-3- carboxamide

1.03 351 H   163- 164 E-13 N-(1-benzyl-1,3- dimethyl- butyl)quinoline-3-carboxamide

1.13 347 H E-14 N-(1-benzyl-1,3- dimethyl-butyl)- 8-chloro- quinoline-3-carboxamide

1.19 381 H   147- 148 E-15 N-(1-benzyl-1,3- dimethyl-butyl)- 8-fluoro-4-methyl- quinoline-3- carboxamide

1.14 379 H 92-94 E-16 N-(1-benzyl- 4,4,4-trifluoro- butyl)-8-fluoro-quinoline-3- carboxamide

1.64 391 H   157- 161 E-17 N-(1-benzyl- 4,4,4-trifluoro-butyl)-8-chloro- quinoline-3- carboxamide

1.75 407 H   163- 167 E-18 N-[2-(2- chlorophenyl)-1- cyano-1-methyl-ethyl]-8-fluoro- quinoline-3- carboxamide

0.96 368-370 G   198- 203 E-19 N-(1-benzyl- 4,4,4-trifluoro-butyl)-8-methyl- quinoline-3- carboxamide

1.79 387 H   158- 161 E-20 N-(1-benzyl-1,3- dimethyl-butyl)- 8-methyl-quinoline-3- carboxamide

1.24 361 H   132- 133 E-21 8-fluoro-N-[1- [(2- fluorophenyl)methyl]-1,3- dimethyl- butyl]quinoline- 3-carboxamide

1.16 383 G   105- 106 E-22 N-[1-[(2- chlorophenyl) methyl]-1,3-dimethyl-butyl]- 8-fluoro- quinoline-3- carboxamide

1.21 399-401 G   109- 110 E-23 N-[1,3-dimethyl- 1-(o-tolylmethyl)butyl]- 8-fluoro- quinoline-3- carboxamide

1.19 379 G   125- 126 E-24 8-fluoro-N-[1- [(4- fluorophenyl)methyl]-1,3- dimethyl- butyl]quinoline- 3-carboxamide

1.15 383 G 38-39 E-25 N-[1-[(4- chlorophenyl) methyl]-1,3-dimethyl-butyl]- quinoline-3- carboxamide

1.21 399-401 G 57-59 E-26 8-fluoro-N-[1- [(3- fluorophenyl) methyl]-1,3-dimethyl- butyl]quinoline- 3-carboxamide

1.15 383 G 45-47 E-27 N-[1-[(3- chlorophenyl) methyl]-1,3-dimethyl-butyl]- 8-fluoro- quinoline-3- carboxamide

1.20 399-401 G 41-42 E-28 N-(1-benzyl-3,3- dimethyl-butyl)- 8-fluoro-quinoline-3- carboxamide

1.10 365 G   178- 180 E-29 N-(1-benzyl-3- methyl-butyl)-8-fluoro-quinoline- 3-carboxamide

1.07 351 G   136- 139 E-30 N-(1-benzyl- 3,3,3-trifluoro-propyl)-8-fluoro- quinoline-3- carboxamide

0.98 377 G   140- 142 E-31 N-[1,3-dimethyl- 1-(p- tolylmethyl)butyl]-8-fluoro- quinoline-3- carboxamide

1.21 379 G   116- 118 E-32 N-[1-[(4- cyanophenyl) methyl]-1,3-dimethyl-butyl]- 8-fluoro- quinoline-3- carboxamide

1.10 390 G 67-69 E-33 N-[1,3-dimethyl- 1-(m- tolylmethyl)butyl]-8-fluoro- quinoline-3- carboxamide

1.20 379 G 94-96 E-34 N-(1-benzyl- 1,3,3-trimethyl- butyl)-8-fluoro-quinoline-3- carboxamide

1.19 379 G 48-50 E-35 N-(1-benzyl-1,3- dimethyl-but-3- enyl)-8-fluoro-quinoline-3- carboxamide

1.12 363 G   115- 117 E-36 N-(1-benzyl-1,3- dimethyl-but-3-enyl)quinoline-3- carboxamide

1.11 345 G    99- 103 E-37 N-(1-benzyl-1- methyl-but-3-enyl)quinoline-3- carboxamide

1.07 331 G E-38 N-(1-benzyl-1- methyl-but-3- enyl)-8-fluoro-quinoline-3- carboxamide

1.08 349 G E-39 N-(1-benzyl- 3,3,3-trifluoro-1- methyl-propyl)-8-fluoro- quinoline-3- carboxamide

1.06 391 G   158- 160 E-40 N-(1-benzyl-1,3- dimethyl-butyl)- 7-fluoro-quinoline-3- carboxamide

1.15 365 G   142- 144 E-41 N-(1-benzyl-1,3- dimethyl-butyl)-1-oxido-quinolin- 1-ium-3- carboxamide

1.06 363 G E-42 N-(1-benzyl-1- methyl-butyl)-8- fluoro-quinoline-3-carboxamide

1.12 351 G E-43 N-(1-benzyl-1- methyl- butyl)quinoline- 3-carboxamide

1.10 333 G E-44 N-[1-[(2- cyanophenyl) methyl]-1,3- dimethyl-butyl]-8-fluoro- quinoline-3- carboxamide

1.10 390 G 43-44 E-45 N-[1-[(3- bromophenyl) methyl]-1,3-dimethyl-butyl]- 8-fluoro- quinoline-3- carboxamide

1.22 443-445 G 87-89 E-46 N-[1-[(3- cyanophenyl) methyl]-1,3-dimethyl-butyl]- 8-fluoro- quinoline-3- carboxamide

1.10 390 G 45-46 E-47 N-[1-benzyl-1- methyl-2-(1- methylcyclopropyl)ethyl]-8- fluoro-quinoline- 3-carboxamide

1.16 377 G   126- 129 E-48 N-(1-benzyl-1,3- dimethyl-butyl)-7,8-difluoro- quinoline-3- carboxamide

1.19 383 G   114- 116 E-49 N-(1-benzyl-2- cyclopropyl-1-methyl-ethyl)-8- fluoro-quinoline- 3-carboxamide

1.11 363 G E-50 N-(1-benzyl-3,3- difluoro-1- methyl-butyl)-8-fluoro-quinoline- 3-carboxamide

1.06 387 G E-51 N-[1- [difluoro(phenyl) methyl]-1,3- dimethyl-but-3-enyl]-8-fluoro- quinoline-3- carboxamide

1.11 399 G E-52 N-(1-benzyl-3,3- difluoro-1- methyl- butyl)quinoline-3-carboxamide

1.05 369 G   131- 133 E-53 N-(1-benzyl-1- cyclopropyl-3- methyl-but-3-enyl)-8-fluoro- quinoline-3- carboxamide

2.01 389 H E-54 N-[1- [difluoro(phenyl) methyl]-1,3- dimethyl-butyl]-8-fluoro- quinoline-3- carboxamide

1.15 401 G E-55 N-(1-benzyl-1,3- dimethyl-but-3- enyl)-7,8- difluoro-quinoline-3- carboxamide

1.16 381 G 94-96 E-56 N-(1-benzyl-3- fluoro-1,3- dimethyl-butyl)-8-fluoro- quinoline-3- carboxamide

1.08 383 G E-57 N-(1-benzyl-3- fluoro-1,3- dimethyl- butyl)quinoline-3-carboxamide

1.07 365 G E-58 N-(1-benzyl-3- hydroxy-1,3- dimethyl-butyl)- 8-fluoro-quinoline-3- carboxamide

1.02 381 G E-59 N-[1- [difluoro(phenyl) methyl]-1,3- dimethyl-butyl]quinoline- 3-carboxamide

1.12 383 G E-60 N-(1-benzyl- 3,3,3-trifluoro-1- methyl-propyl)-8-chloro- quinoline-3- carboxamide

1.11 408 G   141- 144 E-61 N-(1-benzyl- 3,3,3-trifluoro-1-methyl-propyl)- 8-methyl- quinoline-3- carboxamide

1.14 387 G   120- 123 E-62 N-(1-benzyl- 3,3,3-trifluoro-1-methyl-propyl)- 8-cyano- quinoline-3- carboxamide

1.06 398 G   175- 179 E-63 N-(1-benzyl-1,3- dimethyl-butyl)- 6-methoxy-quinoline-3- carboxamide

1.13 377 G   102- 105 E-64 N-(1-benzyl-1,3- dimethyl-butyl)- 5-chloro-quinoline-3- carboxamide

1.23 381-383 G 50-60 E-65 N-(1-benzyl-1,3- dimethyl-butyl)- 7-chloro-quinoline-3- carboxamide

1.22 381-383 G   172- 174 E-66 8-fluoro-N- [3,3,3-trifluoro-1- [(4-fluorophenyl) methyl]-1-methyl- propyl]quinoline- 3-carboxamide

1.07 409 G   146- 147 E-67 N-(1-benzyl-1,3- dimethyl-butyl)- 7-cyano-quinoline-3- carboxamide

1.14 372 G   170- 172 E-68 N-(1-benzyl- 3,3,3-trifluoro-1-methyl-propyl)- 5-chloro- quinoline-3- carboxamide

1.14 407-409 G 85-88 E-69 N-(1-benzyl- 3,3,3-trifluoro-1-methyl-propyl)- 7-chloro- quinoline-3- carboxamide

1.14 407-409 G   174- 176 E-70 N-(1-benzyl- 3,3,3-trifluoro-1-methyl-propyl)- 7-cyano- quinoline-3- carboxamide

1.06 398 G   172- 174 E-71 N-(1-benzyl-1,3- dimethyl-butyl)- 6-methyl-quinoline-3- carboxamide

1.87 361 W E-72 N-(1-benzyl-1,3- dimethyl-butyl)- 7-methyl- quinoline-3-carboxamide

1.84 361 W E-73 N-(1-benzyl-1,3- dimethyl-butyl)- 6-fluoro- quinoline-3-carboxamide

1.86 365 W E-74 N-(1-benzyl-1,3- dimethyl-butyl)- 5-fluoro- quinoline-3-carboxamide

1.89 365 W E-75 N-(1-benzyl-1,3- dimethyl-butyl)- 5-methoxy-quinoline-3- carboxamide

1.82 377 W E-76 N-(1-benzyl-1,3- dimethyl-butyl)- 6-hydroxy-quinoline-3- carboxamide

1.52 363 W E-77 N-(1-benzyl- 3,3,3-trifluoro-1- methyl-propyl)-6-methyl- quinoline-3- carboxamide

1.70 387 W E-78 N-(1-benzyl- 3,3,3-trifluoro-1- methyl-propyl)-6-chloro- quinoline-3- carboxamide

1.81 407 W E-79 N-(1-benzyl- 3,3,3-trifluoro-1- methyl-propyl)-7-methyl- quinoline-3- carboxamide

1.68 387 W E-80 N-(1-benzyl- 3,3,3-trifluoro-1- methyl-propyl)-5-fluoro- quinoline-3- carboxamide

1.72 391 W E-81 N-(1-benzyl- 3,3,3-trifluoro-1- methyl-propyl)-5-methoxy- quinoline-3- carboxamide

1.66 403 W E-82 N-(1-benzyl- 3,3,3-trifluoro-1- methyl-propyl)-6-hydroxy- quinoline-3- carboxamide

1.37 389 W E-83 N-(1-benzyl-1,3- dimethyl-butyl)- 6-chloro- quinoline-3-carboxamide

1.98 381 W E-84 N-(1-benzyl- 3,3,3-trifluoro-1- methyl-propyl)-6-fluoro- quinoline-3- carboxamide

1.69 391 W E-85 N-(1-benzyl-1,3- dimethyl-butyl)- 5-methyl- quinoline-3-carboxamide

1.17 361 G 79-81 E-86 N-(1-benzyl- 3,3,3-trifluoro-1- methyl-propyl)-5-methyl- quinoline-3- carboxamide

1.09 387 G   101- 103 E-87 N-(1-benzyl-1,3- dimethyl-butyl)- 5-hydroxy-quinoline-3- carboxamide

1.01 363 G 90-95 E-88 N-[(E)-1-benzyl- 1-methyl-but-2- enyl]quinoline-3-carboxamide

1.05 331 G E-89 N-(1-benzyl- 3,3,3-trifluoro-1- methyl-propyl)-8-fluoro-2- methyl- quinoline-3- carboxamide

1.09 405 G E-90 N-(1-benzyl- 3,3,3-trifluoro-1- methyl-propyl)-8-fluoro-4- methyl- quinoline-3- carboxamide

1.08 404 G   154- 158 E-91 N-[1-benzyl-1- (trifluoromethyl)butyl]-8-fluoro- quinoline-3- carboxamide

1.15 405 G E-92 N-[1-benzyl-1- (trifluoromethyl) but-3-enyl]-8-fluoro-quinoline- 3-carboxamide

1.13 403 G E-93 N-(1-benzyl- 3,3,3-trifluoro-1- methyl-propyl)-8-chloro-7- fluoro-quinoline- 3-carboxamide

  150- 152 E-94 N-(1-benzyl-3,3- difluoro-1- methyl-allyl)-8-fluoro-quinoline- 3-carboxamide

1.05 371 G    99- 101 E-95 N-(1-benzyl-3,3- difluoro-1- methyl-propyl)-8-fluoro- quinoline-3- carboxamide

1.01 373 G E-96 N-(1-benzyl- 3,3,3-trifluoro-1- methyl-propyl)-4-chloro-8- fluoro-quinoline- 3-carboxamide

1.13 425 G E-97 N-(1-benzyl-3- chloro-3,3- difluoro-1- methyl-propyl)-8-fluoro- quinoline-3- carboxamide

1.10 407-409 G E-98 8-fluoro-N- [3,3,3-trifluoro-1- [(2- fluorophenyl)methyl]-1-methyl- propyl]quinoline- 3-carboxamide

1.07 409 G   131- 133 E-99 8-fluoro-N- [3,3,3-trifluoro-1- [(3-fluorophenyl) methyl]-1-methyl- propyl]quinoline- 3-carboxamide

1.07 409 G   149- 151 E- 100 N-(1-benzyl- 3,3,3-trifluoro-1-methyl-propyl)- 7-fluoro-8- methyl- quinoline-3- carboxamide

1.17 405 G   127- 129 E- 101 N-(1-benzyl-1- ethyl-3,3,3-trifluoro-propyl)- 8-fluoro- quinoline-3- carboxamide

1.11 405 G   127- 129 E- 102 N-(1-benzyl- 3,3,3-trifluoro-1-methyl-propyl)- 7,8-difluoro- quinoline-3- carboxamide

1.10 409 G   158- 160 E- 103 N-[1-benzyl-1- (methoxymethyl)-3-methyl-but-3- enyl]-8-fluoro- quinoline-3- carboxamide

1.13 393 G   147- 149 E- 104 N-(1-benzyl- 3,3,3-trifluoro-1-methyl-propyl)- 8-chloro-4- methyl- quinoline-3- carboxamide

1.13 421 G   184- 186 E- 105 N-(1-benzyl- 3,3,3-trifluoro-1-methyl-propyl)- 8-cyano-4- methyl- quinoline-3- carboxamide

1.07 412 G   194- 197 E- 106 N-(1-benzyl-1,3- dimethyl-butyl)-2-chloro-8- fluoro-quinoline- 3-carboxamide

1.21 399 G   106- 108 E- 107 N-(1-benzyl-1,3- dimethyl-butyl)-8-chloro-4- methyl- quinoline-3- carboxamide

1.21 395-397 G 65-70 E- 108 N-(1-benzyl-1,3- dimethyl-butyl)- 8-cyano-quinoline-3- carboxamide

1.14 372 G   160- 162 E- 109 N-(1-benzyl-1,3- dimethyl-butyl)-8-cyano-4- methyl- quinoline-3- carboxamide

1.15 386 G E- 110 N-(1-benzyl- 3,3,3-trifluoro-1- methyl-propyl)-8-chloro-2- methyl- quinoline-3- carboxamide

1.16 422 G   176- 179 E- 111 N-(1-benzyl-2- cyclobutyl-1- methyl-ethyl)quinoline- 3-carboxamide

1.16 359 G 88-90 E- 112 N-(1-benzyl-2- cyclobutyl-1- methyl-ethyl)-8-fluoro-quinoline- 3-carboxamide

1.18 377 G   125- 127 E- 113 N-(1-benzyl- 3,3,3-trifluoro-1-methyl-propyl)- 8-cyano-2- methyl- quinoline-3- carboxamide

1.10 412 G   136- 140 E- 114 N-(1-benzyl-1,3- dimethyl-butyl)- 8-fluoro-quinoline-3- carbothioamide

1.28 382 G   150- 153 E-115 N-(1-benzyl- 3,3,3-trifluoro-1-methyl-propyl)-8- fluoro-quinoline- 3-carbothioamide

1.19 408 G   173- 175 E- 116 N-(1-benzyl-2,2- diethoxy-1-methyl-ethyl)-8- fluoro-quinoline- 3-carboxamide

1.07 411 G E- 117 N-(1-benzyl-2- methoxyimino-1- methyl-ethyl)-8-fluoro-quinoline- 3-carboxamide

1.01 366 G E- 118 N-(1-benzyl-3- methoxy-1,3- dimethyl-butyl)- 8-fluoro-quinoline-3- carboxamide

1.14 395 G   118- 120 E- 119 N-(1-benzyl-3- hydroxy-1- methyl-propyl)-8-fluoro- quinoline-3- carboxamide

0.88 353 G E- 120 N-(1-benzyl-1- methyl-2-oxo- ethyl)-8-fluoro-quinoline-3- carboxamide

0.92 337 G E- 121 N-(1-benzyl-3- methoxy-1- methyl-propyl)- 8-fluoro-quinoline-3- carboxamide

1.02 367 G E- 122 N-(1-benzyl-1,3- dimethyl-butyl)- 7-methoxy-quinoline-3- carboxamide

1.14 377 G   136- 138 E- 123 N-(1-benzyl-1,3- dimethyl-butyl)-8-methoxy- quinoline-3- carboxamide

1.11 377 G   155- 156 E- 124 N-(1-benzyl-1,3- dimethyl-but-3-enyl)-8-fluoro-2- methyl- quinoline-3- carboxamide

1.14 377 G E- 125 N-(1-benzyl-1,3- dimethyl-butyl)- 2,8-difluoro-quinoline-3- carboxamide

1.23 383 G E- 126 N-(1-benzyl-2- methoxy-1- methyl-ethyl)-8-fluoro-quinoline- 3-carboxamide

1.00 353 G E- 127 N-(1-benzyl-2- ethoxy-1- methyl-ethyl)-8-fluoro-quinoline- 3-carboxamide

1.06 367 G E- 128 N-(1-benzyl-2- isopropoxy-1- methyl-ethyl)-8-fluoro-quinoline- 3-carboxamide

1.13 381 G

TABLE F Physical data of compounds of formula (I) as individualenantiomers RT [M + H] No. IUPAC name STRUCTURE (min) measured [α]_(D)²⁰ method F-1 N-[(1R)-1- benzyl-1,3- dimethyl- butyl]-8-fluoro-quinoline-3- carboxamide

1.32 365  −90.79° SFC: Waters Acquity UPC ²/QDa PDA Detector WatersAcquity UPC ²Column: Daicel SFC CHIRALPAK ® IA, 3 μm, 0.3 cm × 10 cm,40° C. Mobile phase: A: CO₂ B: MeOH gradient: 25% B in 1.8 min ABPR:1800 psi Flow rate: 2.0 ml/min Detection: 240 nm Sample concentration: 1mg/mL in Hept/EtOH 90/10 Injection: 3 μL F-2 N-[(1S)-1- benzyl-1,3-dimethyl- butyl]-8-fluoro- quinoline-3- carboxamide

0.97 365  +92.65° F-3 N-[(1R)-1- benzyl-3- methyl-butyl]- 8-fluoro-quinoline-3- carboxamide

3.43 351 SFC: Waters Acquity UPC ²/QDa PDA Detector Waters Acquity UPC²Column: Daicel SFC CHIRALPAK ® ID 3 μm, 0.3 cm × 10 cm, 40° C. Mobilephase: A: CO₂ B: iPr gradient: 15% B in 4.8 min ABPR: 1800 psi Flowrate: 2.0 ml/min Detection: 235 nm Sample concentration: 1 mg/mL inACN/iPr 50/50 Injection: 1 μL F-4 N-[(1S)-1- benzyl-3- methyl-butyl]-8-fluoro- quinoline-3- carboxamide

2.61 351 F-5 N-[(1R)-1- benzyl-1,3- dimethyl- butyl]quinoline- 3-carboxamide

1.59 348 SFC: Waters Acquity UPC ²/QDa PDA Detector Waters Acquity UPC²Column: Daicel SFC CHIRALPAK ® IA 3 μm, 0.3 cm × 10 cm, 40° C. Mobilephase: A: CO₂ B: EtOH gradient: 30% B in 1.8 min ABPR: 1800 psi Flowrate: 2.0 ml/min Detection: 232 nm Sample concentration: 1 mg/mL inACN/iPr 50/50 Injection: 1 μL F-6 N-[(1S)-1- benzyl-1,3- dimethyl-butyl]quinoline- 3- carboxamide

1.02 348 F-7 N-[(1R)-1-[(2- chlorophenyl) methyl]-1,3- dimethyl-butyl]-8-fluoro- quinoline-3- carboxamide

1.61 399 SFC: Waters Acquity UPC ²/QDa PDA Detector Waters Acquity UPC²Column: Daicel SFC CHIRALPAK ® IA 3 μm, 0.3 cm × 10 cm, 40° C. Mobilephase: A: CO₂ B: MeOH gradient: 20-40% B in 1.8 min ABPR: 1800 psi Flowrate: 2.0 ml/min Detection: 235 nm Sample concentration: 1 mg/mL inACN/iPr 50/50 Injection: 1 μL F-8 N-[(1S)-1-[(2- chlorophenyl)methyl]-1,3- dimethyl- butyl]-8-fluoro- quinoline-3- carboxamide

1.21 399 F-9 N-[(1S)-1- benzyl-1,3- dimethyl-but- 3-enyl]-8- fluoro-quinoline-3- carboxamide

8.10 363 Waters UPLC—Hclass DAD Detector Waters UPLC Column: DaicelCHIRALPAK ® IA, 3 μm, 0.46 cm × 10 cm Mobile phase: Hept/EtOH 80/20 Flowrate: 1.0 ml/min Detection: 235 nm Sample concentration: 1 mg/mL inACN/Hept 50/50 Injection: 2 μL F-10 N-[(1R)-1- benzyl-1,3- dimethyl-but-3-enyl]-8- fluoro- quinoline-3- carboxamide

5.99 363 F-11 N-[(1S)-1- benzyl-3,3,3- trifluoro-1- methyl-propyl]-8-fluoro- quinoline-3- carboxamide

1.70 391 −109.9°  SFC: Waters Acquity UPC ²/QDa PDA Detector WatersAcquity UPC ² Column: Daicel SFC CHIRALPAK ® ID, 3 μm, 0.3 cm × 10 cm,40° C. Mobile phase: A: CO₂ B: iPr gradient: 15% B in 2.8 min ABPR: 1800psi Flow rate: 2.0 ml/min Detection: 235 nm Sample concentration: 1mg/mL in ACN/iPr 50/50 Injection: 1 μL F-12 N-[(1R)-1- benzyl-3,3,3-trifluoro-1- methyl-propyl]- 8-fluoro- quinoline-3- carboxamide

2.16 391 +111.9°  F-13 N-[(1R)-1- benzyl-1,3- dimethyl- butyl]-7-fluoro-quinoline-3- carboxamide

1.53 365 SFC: Waters Acquity UPC ²/QDa PDA Detector Waters Acquity UPC²Column: Daicel SFC CHIRALPAK ® IA, 3 μm, 0.3 cm × 10 cm, 40° C. Mobilephase: A: CO₂ B: MeOH gradient: 20-40% B in 1.8 min ABPR: 1800 psi Flowrate: 2.0 ml/min Detection: 230 nm Sample concentration: 1 mg/mL inACN/iPr 50/50 Injection: 1 μL F-14 N-[(1S)-1- benzyl-1,3- dimethyl-butyl]-7-fluoro- quinoline-3- carboxamide

1.15 365 F-15 N-[(1S)-1- benzyl-1- methyl-but-3- enyl]-8-fluoro-quinoline-3- carboxamide

2.17 349 SFC: Waters Acquity UPC ²/QDa PDA Detector Waters Acquity UPC²Column: Daicel SFC CHIRALPAK ® IA, 3 μm, 0.3 cm × 10 cm, 40° C. Mobilephase: A: CO₂ B: MeOH gradient: 25% B in 4.8 min ABPR: 1800 psi Flowrate: 2.0 ml/min Detection: 235 nm Sample concentration: 1 mg/mL inACN/iPr 50/50 Injection: 1 μL F-16 N-[(1R)-1- benzyl-1- methyl-but-3-enyl]-8-fluoro- quinoline-3- carboxamide

1.58 349 F-17 N-[(1R)-1- benzyl-1,3,3- trimethyl- butyl]-8-fluoro-quinoline-3- carboxamide

1.45 379 SFC: Waters Acquity UPC²/QDa PDA Detector Waters Acquity UPC²Column: Daicel SFC CHIRALPAK ® IA, 3 μm, 0.3 cm × 10 cm, 40° C. Mobilephase: A: CO2 B: MeOH gradient: 25% B in 1.8 min ABPR: 1800 psi Flowrate: 2.0 ml/min Detection: 235 nm Sample concentration: 1 mg/mL inACN/iPr 50/50 Injection: 1 μL F-18 N-[(1S)-1- benzyl-1,3,3- trimethyl-butyl]-8-fluoro- quinoline-3- carboxamide

0.94 379 F-19 N-[(1S)-1- benzyl-1,3- dimethyl-but- 3-enyl]-7,8-difluoro- quinoline-3- carboxamide

4.96 381 Column: Daicel SFC CHIRALPAK ® IA, 3 μm, 0.3 cm × 10 cm, 40° C.Mobile phase: A: CO₂ B: iPr gradient: 15% B in 5.8 min ABPR: 1800 psiFlow rate: 2.0 ml/min Detection: 233 nm Sample concentration: 1 mg/mL inACN/iPr 50/50 Injection: 1 μL F-20 N-[(1R)-1- benzyl-1,3- dimethyl-but-3-enyl]-7,8- difluoro- quinoline-3- carboxamide

4.11 381 F-21 N-[(1R)-1- benzyl-1,3- dimethyl- butyl]-7,8- difluoro-quinoline-3- carboxamide

1.50 383 SFC: Waters Acquity UPC²/QDa PDA Detector Waters Acquity UPC²Column: Daicel SFC CHIRALPAK ® IA, 3 μm, 0.3 cm × 10 cm, 40° C. Mobilephase: A: CO2 B: MeOH gradient: 25% B in 1.8 min ABPR: 1800 psi Flowrate: 2.0 ml/min Detection: 233 nm Sample concentration: 1 mg/mL inACN/iPr 50/50 Injection: 1 μL F-22 N-[(1S)-1- benzyl-1,3- dimethyl-butyl]-7,8- difluoro- quinoline-3- carboxamide

1.09 383 F-23 N-[(1R)-1- benzyl-3- fluoro-1,3- dimethyl-butyl]-8-fluoro- quinoline-3- carboxamide

0.88 383 SFC: IA, 3 μm, 0.3 cm × 10 cm, 40° C. Mobile phase: A: CO₂ B:MeOH gradient: 30% B in 1.8 min ABPR: 1800 psi Flow rate: 2.0 ml/minDetection: 230 nm Sample concentration: 1 mg/mL in ACN/iPr 50/50Injection: 1 μL F-24 N-[(1S)-1- benzyl-3- fluoro-1,3- dimethyl-butyl]-8-fluoro- quinoline-3- carboxamide

1.51 383 F-25 N-[(1S)-1- benzyl-3,3- difluoro-1- methyl-butyl]quinoline- 3- carboxamide

1.81 369 SFC: Waters Acquity UPC²/QDa PDA Detector Waters Acquity UPC²Column: Daicel SFC CHIRALPAK ® IA, 3 μm, 0.3 cm × 10 cm, 40° C. Mobilephase: A: CO2 B: MeOH gradient: 30% B in 1.8 min ABPR: 1800 psi Flowrate: 2.0 ml/min Detection: 230 nm Sample concentration: 1 mg/mL inACN/iPr 50/50 Injection: 1 μL F-26 N-[(1R)-1- benzyl-3,3- difluoro-1-methyl- butyl]quinoline- 3- carboxamide

1.30 369 F-27 N-[(1S)-1- benzyl-3,3,3- trifluoro-1- methyl-propyl]-8-methyl- quinoline-3- carboxamide

0.45 387 SFC: Waters Acquity UPC ²/QDa PDA Detector Waters Acquity UPC ²Column: Daicel SFC CHIRALPAK ® AY, 3 μm, 0.3 cm × 10 cm, 40° C. Mobilephase: A: CO₂ B: EtOH gradient: 30% B in 1.8 min ABPR: 1800 psi Flowrate: 2.0 ml/min Detection: 2338 nm Sample concentration: 1 mg/mL inACN/iPr 50/50 Injection: 1 μL F-28 N-[(1R)-1- benzyl-3,3,3- trifluoro-1-methyl-propyl]- 8-methyl- quinoline-3- carboxamide

1.37 387 F-29 N-[(1S)-1- benzyl-3,3,3- trifluoro-1- methyl-propyl]-8-fluoro-4- methyl- quinoline-3- carboxamide

1.97 405 SFC: Waters Acquity UPC ²/QDa PDA Detector Waters Acquity UPC²Column: Daicel SFC CHIRALPAK ® OZ, 3 μm, 0.3 cm × 10 cm, 40° C. Mobilephase: A: CO₂ B: iPr gradient: 15% B in 1.8 min ABPR: 1800 psi Flowrate: 2.0 ml/min Detection: 220 nm Sample concentration: 1 mg/mL inACN/iPr 50/50 Injection: 1 μL F-30 N-[(1R)-1- benzyl-3,3,3- trifluoro-1-methyl-propyl]- 8-fluoro-4- methyl- quinoline-3- carboxamide

1.03 405 F-31 N-[(1R)-1- benzyl-3,3- difluoro-1- methyl-propyl]-8-fluoro- quinoline-3- carboxamide

1.84 373 SFC: Waters Acquity UPC ²/QDa PDA Detector Waters Acquity UPC ²Column: Daicel SFC CHIRALPAK ® IF, 3 μm, 0.3 cm × 10 cm, 40° C. Mobilephase: A: CO₂ B: MeOH gradient: 30% B in 4.8 min ABPR: 1800 psi Flowrate: 2.0 ml/min Detection: 220 nm Sample concentration: 1 mg/mL inACN/iPr 50/50 Injection: 1 μL F-32 N-[(1S)-1- benzyl-3,3- difluoro-1-methyl-propyl]- 8-fluoro- quinoline-3- carboxamide

1.03 373 F-33 N-[(1S)-1- benzyl-3,3,3- trifluoro-1- methyl-propyl]-8-fluoro-2- methyl- quinoline-3- carboxamide

3.05 405 SFC: Waters Acquity UPC ²/QDa PDA Detector Waters Acquity UPC²Column: Daicel SFC CHIRALPAK ® IC, 3 μm, 0.3 cm × 10 cm, 40° C. Mobilephase: A: CO₂ B: iPR gradient: 10% B in 4.8 min ABPR: 1800 psi Flowrate: 2.0 ml/min Detection: 220 nm Sample concentration: 1 mg/mL inACN/iPr 50/50 Injection: 1 μL F-34 N-[(1R)-1- benzyl-3,3,3- trifluoro-1-methyl-propyl]- 8-fluoro-2- methyl- quinoline-3- carboxamide

3.67 405 F-35 N-[(1S)-1- benzyl-3,3,3- trifluoro-1- methyl-propyl]-8-chloro- quinoline-3- carboxamide

4.99 407 SFC: Waters Acquity UPC ²/QDa PDA Detector Waters Acquity UPC ²Column: Daicel SFC CHIRALPAK ® OZ, 3 μm, 0.3 cm × 10 cm, 40° C. Mobilephase: A: CO₂ B: iPr gradient: 15% B in 2.8 min ABPR: 1800 psi Flowrate: 2.0 ml/min Detection: 237 nm Sample concentration: 1 mg/mL inACN/iPr 50/50 Injection: 1 μL F-36 N-[(1R)-1- benzyl-3,3,3- trifluoro-1-methyl-propyl]- 8-chloro- quinoline-3- carboxamide

1.16 407 F-37 N-[(1S)-1- benzyl-3,3,3- trifluoro-1- methyl-propyl]-7,8-difluoro- quinoline-3- carboxamide

1.05 409 SFC: Waters Acquity UPC ²/QDa PDA Detector Waters Acquity UPC ²Column: Daicel SFC CHIRALPAK ® OZ, 3 μm, 0.3 cm × 10 cm, 40° C. Mobilephase: A: CO₂ B: iPr gradient: 10% B in 2.8 min ABPR: 1800 psi Flowrate: 2.0 ml/min Detection: 233 nm Sample concentration: 1 mg/mL inACN/iPr 50/50 Injection: 1 μL F-38 N-[(1R)-1- benzyl-3,3,3- trifluoro-1-methyl-propyl]- 7,8-difluoro- quinoline-3- carboxamide

1.51 409 F-39 N-[(1S)-1- benzyl-3,3- difluoro-1- methyl-butyl]-8-fluoro- quinoline-3- carboxamide

3.30 387 SFC: Waters Acquity UPC²/QDa PDA Detector Waters Acquity UPC²Column: Daicel SFC CHIRALPAK ® OZ, 3 um, 0.3 cm × 10 cm, 40° C. Mobilephase: A: CO2 B: iPr gradient: 12% B in 4.8 min ABPR: 1800 psi Flowrate: 2.0 ml/min Detection: 234 nm Sample concentration: 1 mg/mL inACN/iPr 50/50 Injection: 1 uL F-40 N-[(1R)-1- benzyl-3,3- difluoro-1-methyl-butyl]- 8-fluoro- quinoline-3- carboxamide

2.10 387

BIOLOGICAL EXAMPLES

Botryotinia fuckeliana (Botrytis cinerea)/Liquid Culture (Gray Mould)

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (Vogels broth). After placing a (DMSO) solution of testcompound into a microtiter plate (96-well format), the nutrient brothcontaining the fungal spores is added. The test plates are incubated at24° C. and the inhibition of growth is determined photometrically 3-4days after application.

The following compounds of Tables E and F gave at least 80% control ofBotryotinia fuckeliana at 200 ppm when compared to untreated controlunder the same conditions, which showed extensive disease development:

-   E-1, E-2, E-3, E-5, E-6, E-7, E-8, E-10, E-11, E-12, E-13, E-14,    E-15, E-16, E-17, E-18, E-19, E-20, E-21, E-22, E-23, E-24, E-25,    E-26, E-27, E-28, E-29, E-30, E-31, E-32, E-33, E-34, E-35, E-36,    E-37, E-38, E-39, E-40, E-41, E-42, E-43, E-44, E-45, E-46, E-47,    E-48, E-49, E-50, E-51, E-52, E-53, E-54, E-55, E-56, E-57, E-58,    E-59, E-60, E-61, E-62, E-63, E-64, E-65, E-66, E-67, E-69, E-70,    E-71, E-72, E-73, E-74, E-75, E-76, E-77, E-79, E-80, E-81, E-82,    E-84, E-85, E-86, E-87, E-88, E-89, E-90, E-91, E-92, E-93, E-94,    E-95, E-96, E-97, E-98, E-99, E-100, E-101, E-102, E-103, E-104,    E-106, E-107, E-109, E-110, E-111, E-112, E-113, E-114, E-115,    E-116, E-117, E-118, E-119, E-121, E-123, E-124, E-125, F-1, F-2,    F-3, F-4, F-5, F-6, F-7, F-8, F-9, F-10, F-11, F-12, F-13, F-14,    F-16, F-17, F-18, F-19, F-20, F-21, F-22, F-23, F-24, F-25, F-26,    F-27, F-28, F-29, F-30, F-31, F-32, F-33, F-34, F-35, F-36, F-37,    F-38, F-39, F-40

Fusarium Culmorum/Liquid Culture (Head Blight)

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of test compound into a microtiter plate (96-well format), thenutrient broth containing the fungal spores is added. The test platesare incubated at 24° C. and the inhibition of growth is determinedphotometrically 3-4 days after application.

The following compounds of Tables E and F gave at least 80% control ofFusarium culmorum at 200 ppm when compared to untreated control underthe same conditions, which showed extensive disease development:

-   E-1, E-2, E-4, E-5, E-6, E-7, E-8, E-10, E-11, E-12, E-13, E-14,    E-15, E-16, E-17, E-18, E-19, E-20, E-21, E-22, E-23, E-24, E-25,    E-26, E-27, E-28, E-29, E-30, E-31, E-32, E-33, E-34, E-35, E-36,    E-37, E-38, E-39, E-40, E-41, E-42, E-43, E-44, E-45, E-46, E-47,    E-48, E-49, E-50, E-51, E-52, E-53, E-54, E-55, E-56, E-57, E-58,    E-59, E-60, E-61, E-62, E-64, E-65, E-66, E-67, E-68, E-69, E-70,    E-71, E-72, E-73, E-74, E-75, E-76, E-77, E-78, E-79, E-80, E-81,    E-82, E-84, E-85, E-86, E-87, E-88, E-89, E-90, E-91, E-92, E-93,    E-94, E-95, E-96, E-97, E-98, E-99, E-100, E-101, E-102, E-103,    E-104, E-105, E-106, E-107, E-109, E-110, E-111, E-112, E-113,    E-114, E-115, E-116, E-117, E-118, E-119, E-120, E-121, E-123,    E-124, E-125, F-1, F-2, F-3, F-4, F-5, F-6, F-7, F-8, F-9, F-10,    F-11, F-12, F-13, F-14, F-16, F-17, F-18, F-19, F-20, F-21, F-22,    F-23, F-24, F-25, F-26, F-27, F-28, F-29, F-30, F-31, F-32, F-33,    F-34, F-35, F-36, F-37, F-38, F-39, F-40    Fusarium culmorum/Wheat/Spikelet Preventative (Head Blight)

Wheat spikelets cv. Monsun are placed on agar in multiwell plates(24-well format) and sprayed with the formulated test compound dilutedin water. The spikelets are inoculated with a spore suspension of thefungus 1 day after application. The inoculated spikelets are incubatedat 20° C. and 60% rh under a light regime of 72 h semi darkness followedby 12 h light/12 h darkness in a climate chamber and the activity of acompound is assessed as percent disease control compared to untreatedwhen an appropriate level of disease damage appears on untreated checkspikelets (6-8 days after application).

The following compounds of Tables E and F gave at least 80% control ofFusarium culmorum at 200 ppm when compared to untreated control underthe same conditions, which showed extensive disease development:

-   E-1, E-5, E-6, E-10, E-11, E-12, E-13, E-15, E-16, E-17, E-19, E-20,    E-21, E-22, E-23, E-24, E-25, E-26, E-28, E-29, E-30, E-35, E-36,    E-38, E-39, E-42, E-43, E-44, E-48, E-49, E-50, E-51, E-52, E-55,    E-56, E-57, E-58, E-59, E-60, E-61, E-62, E-66, E-67, E-69, E-70,    E-71, E-72, E-74, E-75, E-76, E-77, E-79, E-80, E-81, E-82, E-84,    E-85, E-86, E-88, E-89, E-90, E-91, E-92, E-93, E-94, E-95, E-96,    E-97, E-98, E-99, E-100, E-101, E-102, E-103, E-104, E-105, E-106,    E-107, E-109, E-113, E-114, E-125, F-1, F-2, F-3, F-4, F-5, F-9,    F-10, F-11, F-12, F-13, F-14, F-16, F-17, F-18, F-19, F-20, F-21,    F-23, F-24, F-25, F-26, F-27, F-28, F-29, F-31, F-32, F-33, F-35,    F-36, F-37, F-39, F-40    Glomerella lagenarium (Colletotrichum lagenarium)/Liquid Culture    (Anthracnose)

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of test compound into a microtiter plate (96-well format), thenutrient broth containing the fungal spores is added. The test platesare incubated at 24° C. and the inhibition of growth is measuredphotometrically 3-4 days after application.

The following compounds of Tables E and F gave at least 80% control ofGlomerella lagenarium at 200 ppm when compared to untreated controlunder the same conditions, which showed extensive disease development:

-   E-1, E-2, E-5, E-6, E-12, E-13, E-14, E-15, E-20, E-21, E-22, E-23,    E-24, E-25, E-26, E-27, E-28, E-29, E-30, E-31, E-32, E-33, E-34,    E-35, E-36, E-37, E-38, E-39, E-40, E-42, E-43, E-44, E-45, E-46,    E-47, E-48, E-49, E-50, E-51, E-52, E-53, E-54, E-55, E-56, E-57,    E-58, E-60, E-61, E-62, E-66, E-69, E-79, E-86, E-87, E-89, E-90,    E-91, E-92, E-93, E-94, E-95, E-96, E-97, E-98, E-99, E-100, E-101,    E-102, E-103, E-104, E-106, E-111, E-112, E-113, E-114, E-115,    E-118, E-125, F-1, F-2, F-3, F-4, F-5, F-6, F-7, F-8, F-9, F-10,    F-11, F-12, F-13, F-14, F-16, F-17, F-18, F-19, F-20, F-21, F-22,    F-23, F-24, F-25, F-26, F-27, F-28, F-29, F-30, F-31, F-32, F-33,    F-34, F-35, F-36, F-37, F-38, F-39, F-40    Gaeumannomyces graminis/Liquid Culture (Take-All of Cereals)

Mycelial fragments of the fungus from cryogenic storage were directlymixed into nutrient broth (PDB potato dextrose broth). After placing a(DMSO) solution of test compound into a microtiter plate (96-wellformat), the nutrient broth containing the fungal spores iss added. Thetest plates are incubated at 24° C. and the inhibition of growth isdetermined photometrically 4-5 days after application.

The following compounds of Tables E and F gave at least 80% control ofGaeumannomyces graminis at 200 ppm when compared to untreated controlunder the same conditions, which showed extensive disease development:

-   E-1, E-2, E-6, E-7, E-8, E-10, E-13, E-14, E-17, E-19, E-20, E-21,    E-22, E-23, E-24, E-25, E-26, E-27, E-28, E-35, E-37, E-38, E-39,    E-40, E-42, E-43, E-45, E-46, E-47, E-48, E-53, F-1, F-2, F-3, F-4,    F-5, F-6, F-7, F-8, F-10, F-16, F-17, F-18    Monographella nivalis (Microdochium nivale)/Liquid Culture (Foot Rot    Cereals)

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of test compound into a microtiter plate (96-well format), thenutrient broth containing the fungal spores is added. The test platesare incubated at 24° C. and the inhibition of growth is determinedphotometrically 4-5 days after application.

The following compounds of Tables E and F gave at least 80% control ofMonographella nivalis at 200 ppm when compared to untreated controlunder the same conditions, which showed extensive disease development:

-   E-1, E-2, E-5, E-6, E-12, E-13, E-14, E-20, E-21, E-22, E-23, E-24,    E-26, E-27, E-28, E-30, E-31, E-33, E-34, E-35, E-36, E-37, E-38,    E-42, E-43, E-45, E-48, E-49, E-53, E-54, E-55, E-56, E-57, E-58,    E-59, E-60, E-61, E-88, E-92, E-97, E-99, E-103, E-112, E-114,    E-116, E-117, E-118, E-121, E-122, E-123, F-1, F-2, F-4, F-5, F-8,    F-9, F-10, F-18, F-20, F-23, F-24, F-25, F-26, F-27, F-29, F-30,    F-32, F-39    Mycosphaerella arachidis (Cercospora arachidicola)/Liquid Culture    (Early Leaf Spot)

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of test compound into a microtiter plate (96-well format), thenutrient broth containing the fungal spores is added. The test platesare incubated at 24° C. and the inhibition of growth is determinedphotometrically 4-5 days after application.

The following compounds of Tables E and F gave at least 80% control ofMycosphaerella arachidis at 200 ppm when compared to untreated controlunder the same conditions, which showed extensive disease development:

-   E-2, E-35, E-55, F-26    Magnaporthe grisea (Pyricularia oryzae)/Liquid Culture (Rice Blast)

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of test compound into a microtiter plate (96-well format), thenutrient broth containing the fungal spores is added. The test platesare incubated at 24° C. and the inhibition of growth is determinedphotometrically 3-4 days after application.

The following compounds of Tables E and F gave at least 80% control ofMagnaporthe grisea at 200 ppm when compared to untreated control underthe same conditions, which showed extensive disease development:

-   E-5, E-6, E-12, E-14, E-15, E-16, E-17, E-19, E-20, E-21, E-22,    E-23, E-24, E-25, E-26, E-27, E-28, E-29, E-30, E-31, E-32, E-33,    E-34, E-35, E-36, E-37, E-38, E-39, E-40, E-42, E-43, E-44, E-45,    E-46, E-47, E-48, E-49, E-50, E-51, E-52, E-53, E-54, E-55, E-56,    E-57, E-58, E-59, E-60, E-61, E-62, E-65, E-66, E-69, E-114, F-1,    F-37, F-38, F-39, F-40.    Pyrenophora teres/Barley/Leaf Disc Preventative (Net Blotch)

Barley leaf segments cv. Hasso are placed on agar in a multiwell plate(24-well format) and sprayed with the formulated test compound dilutedin water. The leaf segmens are inoculated with a spore suspension of thefungus 2 days after application. The inoculated leaf segments areincubated at 20° C. and 65% rh under a light regime of 12 h light/12 hdarkness in a climate cabinet and the activity of a compound is assessedas disease control compared to untreated when an appropriate level ofdisease damage appears in untreated check leaf segments (5-7 days afterapplication).

The following compounds of Tables E and F gave at least 80% control ofPyrenophora teres at 200 ppm when compared to untreated control underthe same conditions, which showed extensive disease development:

-   E-14, E-26, E-55, E-114    Mycosphaerella graminicola (Septoria tritici)/Liquid Culture    (Septoria Blotch)

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of test compound into a microtiter plate (96-well format), thenutrient broth containing the fungal spores is added. The test platesare incubated at 24° C. and the inhibition of growth is determinedphotometrically 4-5 days after application.

The following compounds of Tables E and F gave at least 80% control ofMycosphaerella graminicola at 200 ppm when compared to untreated controlunder the same conditions, which showed extensive disease development:

-   E-2, E-6, E-55, E-58, E-61, F-2, F-3, F-6, F-24, F-26    Sclerotinia sclerotiorum/Liquid Culture (Cottony Rot)

Mycelia fragments of a newly grown liquid culture of the fungus aredirectly mixed into nutrient broth (Vogels broth). After placing a(DMSO) solution of test compound into a microtiter plate (96-wellformat) the nutrient broth containing the fungal material is added. Thetest plates are incubated at 24° C. and the inhibition of growth isdetermined photometrically 3-4 days after application.

The following compounds of Tables E and F gave at least 80% control ofSclerotinia sclerotiorum at 20 ppm when compared to untreated controlunder the same conditions, which showed extensive disease development:

-   E-6, E-14, E-15, E-20, E-24, E-25, E-26, E-28, E-29, E-34, E-35,    E-36, E-39, E-47, E-114, F-1, F-2, F-3, F-10

1. A compound of formula (I):

wherein X is O or S; R₁ is hydrogen, halogen, methyl, methoxy or cyano;R₂ and R₃ are each independently hydrogen, halogen or methyl; R₄ ishydrogen, cyano, C₁-C₄ alkyl, or C₃-C₄ cycloalkyl, wherein the alkyl andcycloalkyl, may be optionally substituted with 1 to 3 substituentsindependently selected from halogen, cyano, C₁-C₃ alkyl, C₁-C₃ alkoxyand C₁-C₃ alkylthio; R₅ and R₆ are each independently selected fromhydrogen, halogen, C₁-C₄ alkyl, C₁-C₄ alkoxy and C₁-C₄ alkylthio; or R₅and R₆ together with the carbon atom to which they are attachedrepresent C═O, C═NOR_(c), C₃-C₅ cycloalkyl or C₂-C₅ alkenyl, wherein thecycloalkyl and alkenyl may be optionally substituted with 1 to 3substituents independently selected from halogen, cyano, C₁-C₃ alkyl,C₁-C₃ alkoxy and C₁-C₃ alkylthio; R₇ is hydrogen, C₁-C₅ alkyl, C₃-C₅cycloalkyl, C₂-C₅ alkenyl, C₃-C₅ cycloalkenyl, or C₂-C₅ alkynyl, whereinthe alkyl, cycloalkyl, alkenyl, alkynyl, cycloalkenyl may be optionallysubstituted with 1 to 4 substituents independently selected fromhalogen, cyano, C₁-C₃ alkyl, C₁-C₃ alkoxy, hydroxyl and C₁-C₃ alkylthio;R₈ and R₉ are each independently selected from hydrogen, halogen, C₁-C₄alkyl and C₁-C₄ alkoxy; or R₈ and R₉ together with the carbon atom towhich they are attached represent C₃-C₅ cycloalkyl, wherein thecycloalkyl may be optionally substituted with 1 to 3 substituentsindependently selected from halogen, cyano, C₁-C₃ alkyl, C₁-C₃ alkoxyand C₁-C₃ alkylthio; each R₁₀ independently represents halogen, nitro,cyano, formyl, C₁-C₅ alkyl, C₂-C₅ alkenyl, C₂-C₅ alkynyl, C₃-C₆cycloalkyl, C₁-C₅ alkoxy, C₃-C₅ alkenyloxy, C₃-C₅ alkynyloxy, C₁-C₅alkylthio, —C(═NOR_(c))C₁-C₅ alkyl, or C₁-C₅ alkylcarbonyl, wherein thealkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy andalkylthio may be optionally substituted with 1 to 5 substituentsindependently selected from halogen, C₁-C₃ alkyl, C₁-C₃ alkoxy, cyanoand C₁-C₃ alkylthio; n is 0, 1, 2, 3, 4 or 5; each R_(c) isindependently selected from hydrogen, C₁-C₄ alkyl, C₂-C₄ alkenyl, C₃-C₄alkynyl, C₃-C₄ cycloalkyl(C₁-C₂)alkyl and C₃-C₄ cycloalkyl, wherein thealkyl, cycloalkyl, alkenyl and alkynyl groups may be optionallysubstituted with 1 to 3 substituents independently selected from halogenand cyano; R₁₁ is hydrogen, halogen, methyl, methoxy or cyano; R₁₂ andR₁₃ are each independently selected from hydrogen, halogen, methyl,methoxy or hydroxyl; and salts and/or N-oxides thereof; provided thatthe compound is not one of the following compounds:


2. A compound according to claim 1 wherein R₁ is hydrogen, fluoro,chloro, methyl, or cyano.
 3. A compound according to claim 1 wherein R₂and R₃ are each independently hydrogen or methyl.
 4. A compoundaccording to claim 1, wherein R₄ is hydrogen, cyano, C₁-C₃ alkyl, orcyclopropyl, wherein the alkyl and cycloalkyl, may be optionallysubstituted with 1 to 3 substituents independently selected from fluoro,chloro, cyano, methyl, methoxy and methylthio.
 5. A compound accordingto claim 1, wherein R₅ and R₆ are each independently selected fromhydrogen, fluoro, C₁-C₂ alkyl, C₁-C₂ alkoxy and C₁-C₂ alkylthio; or R₅and R₆ together with the carbon atom to which they are attachedrepresent C═O or cyclopropyl, wherein the cyclopropyl may be optionallysubstituted with 1 to 2 substituents independently selected from fluoro,methyl and cyano.
 6. A compound according to claim 1, wherein R₇ isC₁-C₄ alkyl, C₃-C₄ cycloalkyl, C₂-C₄ alkenyl, or C₂-C₃ alkynyl, whereinthe alkyl, cycloalkyl, alkenyl, alkynyl, may be optionally substitutedwith 1 to 3 substituents independently selected from fluoro, chloro,cyano, methyl, hydroxyl and methylthio.
 7. A compound according to claim1 wherein R₈ and R₉ are each independently selected from hydrogen,fluoro, C₁-C₂ alkyl and C₁-C₂ alkoxy; or R₈ and R₉ together with thecarbon atom to which they are attached represent cyclopropyl, whereinthe cyclopropyl may be optionally substituted with 1 to 2 substituentsindependently selected from fluoro, cyano, and methyl.
 8. A compoundaccording to claim 1 wherein each R₁₀ independently represents halogen,cyano, C₁-C₃ alkyl, C₂-C₃ alkenyl, C₂-C₃ alkynyl, cyclopropyl, methoxy,allyloxy, propargyloxy, or C₁-C₂ alkylthio, wherein the alkyl,cyclopropyl, alkenyl, alkynyl, methoxy, allyloxy, propargyloxy andalkylthio may be optionally substituted with 1 to 3 substituentsindependently selected from fluoro, chloro, methyl, and cyano; n is 0,1, 2 or
 3. 9. A compound according to claim 1 wherein R₁₁ is hydrogen,fluoro, chloro, methyl or cyano; and R₁₂ and R₁₃ are each independentlyselected from hydrogen, fluoro, methyl and hydroxyl.
 10. A compoundaccording to claim 1 wherein X is O or S; R₁ is hydrogen, fluoro,chloro, methyl, or cyano; R₂ and R₃ are each independently hydrogen ormethyl; R₄ is hydrogen, cyano, C₁-C₃ alkyl, or cyclopropyl, wherein thealkyl and cycloalkyl, may be optionally substituted with 1 to 3substituents independently selected from fluoro, chloro, cyano, methyl,methoxy, and methylthio; R₅ and R₆ are each independently selected fromhydrogen, fluoro, C₁-C₂ alkyl, C₁-C₂ alkoxy and C₁-C₂ alkylthio; or R₅and R₆ together with the carbon atom to which they are attachedrepresent C═O or cyclopropyl, wherein the cyclopropyl may be optionallysubstituted with 1 to 2 substituents independently selected from fluoro,methyl and cyano; R₇ is C₁-C₄ alkyl, C₃-C₄ cycloalkyl, C₂-C₄ alkenyl, orC₂-C₃ alkynyl, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, may beoptionally substituted with 1 to 3 substituents independently selectedfrom fluoro, chloro, cyano, methyl, hydroxyl and methylthio; R₈ and R₉are each independently selected from hydrogen, fluoro, C₁-C₂ alkyl andC₁-C₂ alkoxy; or R₈ and R₉ together with the carbon atom to which theyare attached represent cyclopropyl, wherein the cyclopropyl may beoptionally substituted with 1 to 2 substituents independently selectedfrom fluoro, cyano, and methyl; each R₁₀ independently representshalogen, cyano, C₁-C₃ alkyl, C₂-C₃ alkenyl, C₂-C₃ alkynyl, cyclopropyl,methoxy, allyloxy, propargyloxy, or C₁-C₂ alkylthio, wherein the alkyl,cyclopropyl, alkenyl, alkynyl, methoxy, allyloxy, propargyloxy andalkylthio may be optionally substituted with 1 to 3 substituentsindependently selected from fluoro, chloro, methyl, and cyano; n is 0,1, 2 or 3; R₁₁ is hydrogen, fluoro, chloro, methyl or cyano; and R₁₂ andR₁₃ are each independently selected from hydrogen, fluoro, methyl andhydroxyl; or a salt or N-oxide thereof.
 11. A compound according toclaim 1 wherein X is O or S; R₁ is hydrogen, fluoro, methyl, or cyano;R₂ is hydrogen and R₃ is hydrogen or methyl; or R₂ is hydrogen or methyland R₃ is hydrogen; R₄ is hydrogen, cyano, methyl or ethyl, wherein themethyl and ethyl may be optionally substituted with 1 to 3 substituentsindependently selected from fluoro and methoxy; R₅ and R₆ are eachindependently selected from hydrogen, fluoro, methyl, methoxy andmethylthio; or R₅ and R₆ together with the carbon atom to which they areattached represent cyclopropyl; R₇ is C₁-C₄ alkyl, C₃-C₄ cycloalkyl, orC₂-C₄ alkenyl, wherein the alkyl, cycloalkyl and alkenyl may beoptionally substituted with 1 to 3 substituents independently selectedfrom fluoro, chloro, hydroxyl, cyano and methyl; R₈ and R₉ are eachindependently selected from hydrogen, fluoro and methyl; or R₈ and R₉together with the carbon atom to which they are attached representcyclopropyl; each R₁₀ independently represents fluoro, chloro, cyano,methyl, cyclopropyl, methoxy or methylthio, wherein the methyl,cyclopropyl, methoxy and methylthio may be optionally substituted with 1to 3 substituents independently selected from fluoro and chloro; n is 0,1 or 2; R₁₁ is hydrogen, fluoro, methyl or chloro; and R₁₂ and R₁₃ areeach independently selected from hydrogen, fluoro and methyl; or a saltor N-oxide thereof.
 12. A compound according to claim 1 wherein X is Oor S; R₁ is hydrogen or fluoro; R₂ and R₃ are both hydrogen; R₄ ismethyl or ethyl (wherein the methyl and ethyl may be optionallysubstituted with 1 to 3 fluoro substituents); R₅ and R₆ are eachindependently selected from hydrogen and fluoro; R₇ is methyl, ethyl,n-propyl, iso-propyl, sec-butyl, tert-butyl, C₃-C₄ cycloalkyl, or C₂-C₄alkenyl, wherein the methyl, ethyl, n-propyl, iso-propyl, sec-butyl,tert-butyl, cycloalkyl and alkenyl may be optionally substituted with 1to 3 substituents independently selected from fluoro, chloro and methyl;R₈ and R₉ are each independently selected from hydrogen or fluoro; eachR₁₀ independently represents fluoro, chloro, cyano or methyl, whereinthe methyl may be optionally substituted with 1 to 3 fluorosubstituents; n is 0, 1 or 2; and R₁₁ is hydrogen or fluoro; R₁₂ and R₁₃are both hydrogen; or a salt or N-oxide thereof.
 13. A compoundaccording to claim 1 wherein X is O.
 14. A composition comprising afungicidally effective amount of a compound of formula as defined inclaim
 1. 15. A composition according to claim 14, wherein thecomposition further comprises at least one additional active ingredientand/or a diluent.
 16. A method of combating, preventing or controllingphytopathogenic diseases which comprises applying to a phytopathogen, tothe locus of a phytopathogen, or to a plant susceptible to attack by aphytopathogen, or to propagation material thereof, a fungicidallyeffective amount of a compound of formula (I) as defined in claim 1 or acomposition comprising a fungicidally effective amount of a compound offormula (I) as defined in claim 1.